JP2015027934A - Manufacturing method of nitrogen-containing carbon alloy, nitrogen-containing carbon alloy, and fuel cell catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nitrogen-containing carbon alloy having an unprecedentedly high oxidation-reduction activity and a method for manufacturing the same.SOLUTION: The present invention concerns a manufacturing method of a nitrogen-containing carbon alloy including a step of firing a precursor including: at least one type selected from among heterocyclic aromatic compounds possessing nitrogen-containing aromatic groups expressed by the following general formula (1), salts thereof, and hydrates thereof; and an inorganic metal salt: [in the general formula (1), A expresses an atomic group constituted by a 5- to 11-membered non-condensed heteroaromatic rings; L expresses a single bond or (x+1)-valent linkage group; B expresses a hydrogen atom, substituted or unsubstituted aromatic group, or substituted or unsubstituted nitrogen-containing aromatic group, where at least one member of B is a substituted or unsubstituted nitrogen-containing aromatic group; within the at least one nitrogen-containing aromatic group, either or both of 3- and 4-position ring skeleton constituent atoms adjacent to the coupling site with L are nitrogen atoms].

Description

  The present invention relates to a method for producing a nitrogen-containing carbon alloy, a nitrogen-containing carbon alloy, and a fuel cell catalyst. Specifically, the present invention relates to a method for producing a nitrogen-containing carbon alloy including a step of firing a precursor containing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt, a nitrogen-containing carbon alloy, and a nitrogen-containing compound. Fuel cell catalyst using carbon alloy

Conventionally, a noble metal catalyst using platinum (Pt), palladium (Pd), etc. is used as a catalyst having a high oxygen reduction activity, for example, for a solid polymer electrolyte fuel cell used in automobiles, household electric heat supply systems, etc. Has been. However, since such noble metal-based catalysts are expensive, it is difficult to further spread them.
For this reason, technological development of a catalyst in which platinum is greatly reduced or a catalyst formed without using platinum is being promoted.

  A carbon catalyst is known as a catalyst that can be formed without using platinum, and a nitrogen-containing carbon alloy obtained by heat-treating a nitrogen-containing compound is used as a carbon catalyst. For example, Patent Document 1 discloses a polymer electrolyte fuel cell catalyst comprising a composite of an s-triazine ring derivative and a metal. Patent Document 2 discloses a nitrogen-containing carbon alloy catalyst produced by firing a nitrogen-containing heterocyclic compound having a molecular weight of 60 to 2000 and an inorganic metal or inorganic metal salt.

Non-patent document 1 discloses a non-platinum catalyst for a fuel cell prepared by heating and firing a mixture of _2- pyridyltriazine Fe complex [Fe (TPTZ) ₂ ] supported on carbon. Here, it is proposed to fire a mixture of 2-pyridyltriazine and a metal complex, and there is no description about using an inorganic metal or firing an inorganic metal.

JP 2007-175578 A JP 2011-225431-A

Bezerra, Cicero WB; Zhang, Lei; Lee, Kunchan; Liu, Hansan; Zhang, Jianlu; Shi, Zheng; Marques, Aldalea LB; Marques, Edmar P .; Wu, Shaohong; Zhang, Jiujun, Electrochimica Acta (2008), 53 (26), 7703-7710.

As described above, the nitrogen-containing carbon alloy catalyst containing a nitrogen-containing compound can exhibit catalytic activity without using platinum. However, recent applications such as fuel cells are required to have higher oxygen reduction activity, and the oxygen reduction activity of conventional carbon catalysts may be insufficient. For this reason, it has been desired to produce a nitrogen-containing carbon alloy that can exhibit higher oxygen reduction activity.
Moreover, in the conventional method for producing a nitrogen-containing carbon alloy using a nitrogen-containing compound, the yield is poor, and further improvement in productivity has been demanded.

  In order to solve the problems of the prior art, the present inventors have proceeded with studies for the purpose of producing a nitrogen-containing carbon alloy having higher oxygen reduction activity. Furthermore, the present inventors have studied for the purpose of increasing the yield of nitrogen-containing carbon alloy and increasing productivity.

As a result of intensive studies to solve the above problems, the present inventors calcined a precursor containing a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure and an inorganic metal salt, It has been found that the oxygen reduction activity can be sufficiently increased by producing a nitrogen-containing carbon alloy. Furthermore, the present inventors succeeded in increasing the yield of nitrogen-containing carbon alloy, and completed the present invention.
Specifically, the present invention has the following configuration.

一般式（１）中、Ａは５〜１１員の非縮合複素芳香環から構成される原子団を表し、Ｌは単結合または（ｘ＋１）価の連結基を表し、Ｂは水素原子、置換または無置換の芳香族基、又は置換または無置換の含窒素芳香族基を表し、少なくとも１つのＢは、置換または無置換の含窒素芳香族基であり、含窒素芳香族基の少なくとも１つにおいて、Ｌとの結合部位に対して３位及び４位の環骨格構成原子のいずれか一方又は両方は窒素原子である。Ａの非縮合複素芳香環におけるヘテロ原子数は、Ｂの含窒素芳香族基１つ当たりにおけるヘテロ原子数と同じであるか又は多い。また、ｘおよびｙはそれぞれ独立に１以上の整数を表す。
［２］一般式（１）において、ｘは１〜３の整数を表し、ｙは１〜５の整数を表す［１］に記載の含窒素カーボンアロイの製造方法。
［３］一般式（１）で表される含窒素芳香族基を有する複素芳香環化合物は、下記一般式（２）で表される［１］または［２］に記載の含窒素カーボンアロイの製造方法；

一般式（２）中、Ｑ¹〜Ｑ³はそれぞれ独立にヘテロ原子又は炭素原子を表し、Ｑ¹〜Ｑ³のうち少なくとも１つは窒素原子であり、ｂ１〜ｂ３はそれぞれ独立に水素原子、置換または無置換の芳香族基、又は置換または無置換の含窒素芳香族基を表し、ｂ１〜ｂ３の少なくともいずれか１つは置換または無置換の含窒素芳香族基であり、含窒素芳香族基の少なくとも１つにおいて、結合部位に対して３位及び４位の環骨格構成原子のいずれか一方又は両方は窒素原子である。Ｑ¹〜Ｑ³を含む非縮合複素芳香環におけるヘテロ原子数は、ｂ１〜ｂ３の含窒素芳香族基１つ当たりにおけるヘテロ原子数と同じであるか又は多い。
［４］一般式（２）において、Ｑ¹〜Ｑ³は窒素原子である［３］に記載の含窒素カーボンアロイの製造方法。
［５］一般式（２）において、ｂ１〜ｂ３は６員の置換または無置換の含窒素芳香族基である［３］または［４］に記載の含窒素カーボンアロイの製造方法。
［６］一般式（２）において、ｂ１〜ｂ３はピリジル基またはピリミジル基である［３］〜［５］のいずれかに記載の含窒素カーボンアロイの製造方法。
［７］含窒素芳香族基を有する複素芳香環化合物は、下記式（３）または（４）で表される化合物である［１］〜［６］のいずれかに記載の含窒素カーボンアロイの製造方法。

［８］一般式（１）で表される含窒素芳香族基を有する複素芳香環化合物は、下記一般式（５）で表される［１］または［２］に記載の含窒素カーボンアロイの製造方法；

一般式（５）中、Ａは５〜１１員の非縮合複素芳香環から構成される原子団を表し、Ｌは単結合、または（ｘ＋１）価の連結基を表し、Ｂは水素原子、置換または無置換の芳香族基、又は置換または無置換の含窒素芳香族基であり、少なくとも１つのＢは、置換または無置換の含窒素芳香族基であり、含窒素芳香族基の少なくとも１つにおいて、Ｌとの結合部位に対して３位及び４位の環骨格構成原子のいずれか一方又は両方は窒素原子である。Ａの非縮合複素芳香環におけるヘテロ原子数は、Ｂの含窒素芳香族基１つ当たりにおけるヘテロ原子数と同じであるか又は多い。また、ｘは１以上の整数を表す。
［９］一般式（５）において、ｘは１〜５の整数を表す［８］に記載の含窒素カーボンアロイの製造方法。
［１０］含窒素芳香族基を有する複素芳香環化合物は、下記化合物群より選択される化合物である［１］または［２］に記載の含窒素カーボンアロイの製造方法。

［１１］無機金属塩は、無機金属塩化物である［１］〜［１０］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１２］無機金属塩の金属種が、ＦｅまたはＣｏである［１］〜［１１］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１３］無機金属塩は、含水塩である［１］〜［１２］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１４］有機金属錯体をさらに含む［１］〜［１３］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１５］有機金属錯体は、金属アセタート錯体、またはβ−ジケトン金属錯体である［１４］に記載の含窒素カーボンアロイの製造方法。
［１６］有機金属錯体は、アセチルアセトン鉄（ＩＩ）錯体である［１４］または［１５］に記載の含窒素カーボンアロイの製造方法。
［１７］焼成する工程は、前駆体を４００℃以上で焼成する工程である［１］〜［１６］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１８］焼成する工程は、前駆体を７００〜１０００℃で焼成する工程である［１］〜［１７］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１９］焼成する工程の前に、前駆体を粉砕する工程をさらに含む［１］〜［１８］のいずれかに記載の含窒素カーボンアロイの製造方法。
［２０］焼成する工程の後に、焼成された含窒素カーボンアロイを酸で洗浄する酸洗浄工程を含む［１］〜［１９］のいずれかに記載の含窒素カーボンアロイの製造方法。
［２１］焼成する工程の後に、焼成された含窒素カーボンアロイを粉砕する工程と、再焼成する工程とをさらに含む［１］〜［２０］のいずれかに記載の含窒素カーボンアロイの製造方法。
［２２］再焼成する工程は、１０００〜１５００℃で焼成する工程である［２１］に記載の含窒素カーボンアロイの製造方法。
［２３］再焼成する工程の前に、脱気及び窒素置換する工程をさらに含む［２１］又は［２２］に記載の含窒素カーボンアロイの製造方法。
［２４］［１］〜［２３］のいずれかに記載の方法で製造された含窒素カーボンアロイ。
［２５］［２４］に記載の含窒素カーボンアロイを用いた燃料電池触媒。 [1] A precursor containing an inorganic metal salt and at least one selected from a heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the following general formula (1), a salt thereof and a hydrate thereof is calcined. A method for producing a nitrogen-containing carbon alloy comprising a step;

In general formula (1), A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring, L represents a single bond or a (x + 1) -valent linking group, and B represents a hydrogen atom, a substituted or Represents an unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups , Any one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X and y each independently represents an integer of 1 or more.
[2] The method for producing a nitrogen-containing carbon alloy according to [1], wherein in General Formula (1), x represents an integer of 1 to 3, and y represents an integer of 1 to 5.
[3] The heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is a nitrogen-containing carbon alloy according to [1] or [2] represented by the following general formula (2). Production method;

In General Formula (2), Q ^{1 to} Q ³ each independently represents a hetero atom or a carbon atom, at least one of Q ^{1 to} Q ³ is a nitrogen atom, b1 to b3 are each independently a hydrogen atom, Represents a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of b1 to b3 is a substituted or unsubstituted nitrogen-containing aromatic group, and a nitrogen-containing aromatic group In at least one of the groups, one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the binding site are nitrogen atoms. Q Number heteroatoms in non-fused heteroaromatic ring containing ¹ to Q ³ is or greater identical to the number of heteroatoms in the nitrogen-containing aromatic group per one of b1 to b3.
[4] The method for producing a nitrogen-containing carbon alloy according to [3], wherein in the general formula (2), Q ^{1 to} Q ³ are nitrogen atoms.
[5] The method for producing a nitrogen-containing carbon alloy according to [3] or [4], wherein in general formula (2), b1 to b3 are 6-membered substituted or unsubstituted nitrogen-containing aromatic groups.
[6] The method for producing a nitrogen-containing carbon alloy according to any one of [3] to [5], wherein b1 to b3 are a pyridyl group or a pyrimidyl group in the general formula (2).
[7] The heteroaromatic ring compound having a nitrogen-containing aromatic group is a compound represented by the following formula (3) or (4), the nitrogen-containing carbon alloy according to any one of [1] to [6] Production method.

[8] The heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is a nitrogen-containing carbon alloy according to [1] or [2] represented by the following general formula (5). Production method;

In general formula (5), A represents an atomic group composed of a 5- to 11-membered non-condensed heteroaromatic ring, L represents a single bond or a (x + 1) -valent linking group, B represents a hydrogen atom, substituted Or an unsubstituted aromatic group or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups In the above, any one or both of the ring skeleton constituting atoms at the 3rd and 4th positions relative to the bonding site with L are nitrogen atoms. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X represents an integer of 1 or more.
[9] The method for producing a nitrogen-containing carbon alloy according to [8], wherein x in the general formula (5) represents an integer of 1 to 5.
[10] The method for producing a nitrogen-containing carbon alloy according to [1] or [2], wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group is a compound selected from the following compound group.

[11] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [10], wherein the inorganic metal salt is an inorganic metal chloride.
[12] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [11], wherein the metal species of the inorganic metal salt is Fe or Co.
[13] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [12], wherein the inorganic metal salt is a hydrate salt.
[14] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [13], further comprising an organometallic complex.
[15] The method for producing a nitrogen-containing carbon alloy according to [14], wherein the organometallic complex is a metal acetate complex or a β-diketone metal complex.
[16] The method for producing a nitrogen-containing carbon alloy according to [14] or [15], wherein the organometallic complex is an acetylacetone iron (II) complex.
[17] The step of firing is the method for producing a nitrogen-containing carbon alloy according to any one of [1] to [16], which is a step of firing the precursor at 400 ° C. or higher.
[18] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [17], wherein the firing step is a step of firing the precursor at 700 to 1000 ° C.
[19] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [18], further including a step of pulverizing the precursor before the step of firing.
[20] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [19], including an acid washing step of washing the fired nitrogen-containing carbon alloy with an acid after the firing step.
[21] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [20], further comprising a step of pulverizing the fired nitrogen-containing carbon alloy and a step of re-firing after the step of firing. .
[22] The method for producing a nitrogen-containing carbon alloy according to [21], wherein the re-baking step is a step of baking at 1000 to 1500 ° C.
[23] The method for producing a nitrogen-containing carbon alloy according to [21] or [22], further including a step of deaeration and nitrogen substitution before the step of refiring.
[24] A nitrogen-containing carbon alloy produced by the method according to any one of [1] to [23].
[25] A fuel cell catalyst using the nitrogen-containing carbon alloy according to [24].

According to the production method of the present invention, a nitrogen-containing carbon alloy having a sufficiently high oxygen reduction activity can be obtained. For this reason, the nitrogen-containing carbon alloy obtained by the production method of the present invention can be used as a carbon catalyst, and such a carbon catalyst is preferably used for a fuel cell or an environmental catalyst.
Moreover, according to the manufacturing method of this invention, the yield of a nitrogen-containing carbon alloy can be raised and productivity can be improved.

It is a schematic block diagram of the fuel cell using the nitrogen-containing carbon alloy of this invention. It is a schematic block diagram of the electric double layer capacitor using the nitrogen-containing carbon alloy of this invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The present invention includes a step of firing a precursor containing an inorganic metal salt and at least one selected from a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure, a salt thereof and a hydrate thereof. The present invention relates to a method for producing a nitrogen carbon alloy. Below, the hetero aromatic ring compound which has a nitrogen-containing aromatic group, an inorganic metal salt, etc. are demonstrated in detail.

<Heteroaromatic ring compound having nitrogen-containing aromatic group>
The heteroaromatic ring compound having a nitrogen-containing aromatic group used in the present invention is represented by the following general formula (1). Note that the heteroaromatic ring compound having a nitrogen-containing aromatic group includes salts thereof or hydrates thereof.

  In general formula (1), A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring, and L represents a single bond or a (x + 1) -valent linking group. B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, In at least one of the group groups, either one or both of the ring skeleton constituent atoms at the 3rd and 4th positions relative to the bonding site with L is a nitrogen atom. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X and y each independently represents an integer of 1 or more.

  In the general formula (1), A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring. Here, the non-fused heteroaromatic ring is a heteroaromatic ring having no fused ring, and the atomic group composed of such a non-fused heteroaromatic ring has at least one non-fused heteroaromatic ring. The atomic group composed of a non-fused heteroaromatic ring may be composed of two or more non-fused heteroaromatic rings, but is preferably composed of one non-fused heteroaromatic ring. The number of ring members of one non-fused heteroaromatic ring may be 5 to 11, preferably 5 to 10, more preferably 5 to 8, and still more preferably 5 or 6.

  Examples of the hetero atom constituting the 5- to 11-membered non-condensed heteroaromatic ring include 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the non-fused heteroaromatic ring include a pyridine ring, a pyrimidine ring, a triazine ring, an imidazole ring, a pyrroline ring, an imidazole group, a furan ring, and a thiophene ring. Among them, a pyridine ring, a pyrimidine ring, and a triazine ring Preferred examples include an imidazole ring and a pyrroline ring.

In the general formula (1), L represents a single bond or a (x + 1) -valent linking group.
The (x + 1) -valent linking group includes a substituted or unsubstituted aromatic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted cycloalkylene _{group, -CO -, - CO 2 -} , - O -, - NH -, - SO -, - SO 2 -, - S -, - CONH -, - NHCO-, or a combination thereof from x-1 single An x + 1 valent group excluding any hydrogen atom is preferred.
The aromatic group preferably has 6 to 20 carbon atoms, more preferably a phenylene group, a biphenylene group, or a naphthylene group, further preferably a phenylene group or a biphenylene group, and more preferably a phenylene group. Particularly preferred.
The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The alkynylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The cycloalkylene group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, still more preferably 5 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms.
When having a substituent, the substituent includes a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), hydroxy group, cyano group, aliphatic group (aralkyl group, cycloalkyl group, active methine group, etc. ), Vinyl group, allyl group, acetylenyl group, aryl group (regardless of the position of substitution), acyl group, aliphatic oxy group (alkoxy group, alkyleneoxy group, ethyleneoxy group or propyleneoxy group unit repeatedly containing Aryloxy group, heterocyclic oxy group, aliphatic carbonyl group, arylcarbonyl group, heterocyclic carbonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, sulfonylcarbamoyl group , Acylcarbamoyl group, sulfamoylcarba Yl group, thiocarbamoyl group, aliphatic carbonyloxy group, aryloxycarbonyloxy group, heterocyclic carbonyloxy group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, acylamino group, aliphatic oxyamino group , Aryloxyamino group, sulfamoylamino group, acylsulfamoylamino group, oxamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, carbamoylamino group, mercapto group , Aliphatic thio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, sulfamoyl group, aliphatic sulfonylureido group, aryl Sulfonylureido group, heterocyclic sulfonylureido group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfamoyl group, arylsulfamoyl group, heterocyclic sulfamoyl group, acylsulfamoyl group Sulfonylsulfamoyl group or a salt thereof, carbamoylsulfamoyl group, sulfonamido group, aliphatic ureido group, arylureido group, heterocyclic ureido group, aliphatic sulfonamido group, arylsulfonamido group, heterocyclic sulfonamido group , Aliphatic sulfinyl group, arylsulfinyl group, nitro group, nitroso group, diazo group, azo group, hydrazino group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, silyl group (for example, trimethylsilyl) , T-butyldimethylsilyl, phenyldimethylsilyl), silyloxy groups (eg trimethylsilyloxy, t-butyldimethylsilyloxy), borono groups, ionic hydrophilic groups (eg carboxyl groups, sulfo groups, phosphono groups and quaternary ammonium) Group) and the like. Among these, a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), a vinyl group, an allyl group, an acetylenyl group, an aryl group (regarding the position of substitution) and an amino group are preferable as a substituent.
For example, when x is 1, L represents a single bond or a divalent linking group, and when x is 2, L represents a trivalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted group. biphenylene group, a substituted or unsubstituted naphthylene _{group, -CO -, - CO 2 -} , - O -, - NH -, - SO -, - SO 2 -, - S -, - CONH -, - NHCO- , etc. Can be mentioned. Examples of the trivalent linking group include, for example,>CH—,> N—, a group obtained by removing one hydrogen atom from a group having a substituent among the groups listed as examples of the divalent linking group, and the like. Can be mentioned. L may be a group obtained by combining two or more of the above linking groups. For example, a combination of two or more substituted or unsubstituted alkylene groups, alkenylene groups, and alkynylene groups, or a combination of two or more substituted or unsubstituted alkylene groups, alkenylene groups, alkynylene groups, and substituted or unsubstituted phenylene groups. It can be based. When there are a plurality of L, the plurality of L may be the same or different.
Examples of the (x + 1) -valent linking group include a phenylene group, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, —CO ₂ —, —CONH—, — O- or a x + 1 valent group in which x-1 arbitrary hydrogen atoms are removed from a combination thereof, a phenylene group, an alkylene group having 1 to 4 carbon atoms, and an alkenylene group having 2 to 6 carbon atoms , An alkynylene group having 2 to 6 carbon atoms, —CONH—, or a combination of x + 1 valences in which x−1 arbitrary hydrogen atoms are removed from a combination thereof is more preferable.

In the general formula (1), B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group Represents a group. Here, the nitrogen-containing aromatic group means a group having a nitrogen atom as a constituent atom of the aromatic group. When a plurality of B are present, at least one of the Bs may be a substituted or unsubstituted nitrogen-containing aromatic group, but it is preferable that all Bs are substituted or unsubstituted nitrogen-containing aromatic groups. The nitrogen-containing aromatic group is preferably a pyridyl group, a pyrimidyl group, a triazyl group, or an imidazolyl group. A plurality of B may be the same or different.
B is preferably a hydrogen atom, a phenyl group, a pyridyl group, a pyrimidyl group, a triazine group, or an imidazolyl group. When B is an aromatic group, the number of carbon atoms is preferably 6 to 14, more preferably 6 to 10, and particularly preferably a phenyl group. At least one B is a nitrogen-containing aromatic group. In this case, it is preferably 5 to 11 members, more preferably 5 to 8 members, more preferably 5 or 6 members, and a pyridyl group. , A pyrimidyl group, a triazine group, or an imidazolyl group is particularly preferable.

When the aromatic group or nitrogen-containing aromatic group represented by B has a substituent, specific examples of preferable substituents include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), a hydroxy group, and a cyano group. , Aliphatic groups (including aralkyl groups, cycloalkyl groups, active methine groups, etc.), vinyl groups, allyl groups, acetylenyl groups, aryl groups (regardless of the position of substitution), acyl groups, aliphatic oxy groups (alkoxy groups) Or an aryloxy group, a heterocyclic oxy group, an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, an aliphatic oxycarbonyl group. , Aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, sulfonylcal Moyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, thiocarbamoyl group, aliphatic carbonyloxy group, aryloxycarbonyloxy group, heterocyclic carbonyloxy group, amino group, aliphatic amino group, arylamino group, heterocyclic amino Group, acylamino group, aliphatic oxyamino group, aryloxyamino group, sulfamoylamino group, acylsulfamoylamino group, oxamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxy Carbonylamino group, carbamoylamino group, mercapto group, aliphatic thio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, Rufamoyl group, aliphatic sulfonylureido group, arylsulfonylureido group, heterocyclic sulfonylureido group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfamoyl group, arylsulfamoyl group , Heterocyclic sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, carbamoylsulfamoyl group, sulfonamido group, aliphatic ureido group, arylureido group, heterocyclic ureido group, aliphatic sulfonamido group , Arylsulfonamide group, heterocyclic sulfonamido group, aliphatic sulfinyl group, arylsulfinyl group, nitro group, nitroso group, diazo group, azo group, hydrazino group, dialiphatic oxyphosphinyl group, diaryl Oxyphosphinyl group, silyl group (eg trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), silyloxy group (eg trimethylsilyloxy, t-butyldimethylsilyloxy), borono group, ionic hydrophilic group (eg carboxyl Group, sulfo group, phosphono group and quaternary ammonium group).
Substituents containing unsaturated groups are more preferred, vinyl group, allyl group, acetylenyl group, aryl group (phenyl group, naphthyl group, phenanthrene group, anthracenyl group, triphenyl group, pyrenyl group, perylenyl group, benzhydryl group, benzyl group. Group, cinamyl group, cumenyl group, methicyl group, phenylethyl group, styryl group, tolyl group, trityl group, xylyl group). These substituent groups may be further substituted, and examples of the further substituent include groups selected from the substituents and heteroaromatic groups described above (regardless of the position of substitution).

In at least one of the nitrogen-containing aromatic groups, either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms. In the present invention, in at least one of the nitrogen-containing aromatic groups, either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L may be a nitrogen atom, In all of the nitrogen-containing aromatic groups, it is more preferable that either one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the bonding site with L is a nitrogen atom. In the nitrogen-containing aromatic group, it is preferable that only the ring skeleton constituting atom at the 3rd or 4th position with respect to the bonding position with L is a nitrogen atom, but the ring skeleton constituting atom other than the corresponding site is a nitrogen atom. May be. For example, the ring skeleton constituent atoms at the 3rd and 1st positions relative to the bond position with L are nitrogen atoms, the ring skeleton constituent atoms at the 3rd and 2nd positions are nitrogen atoms, or the 4th and 2nd positions. The ring skeleton constituent atom may be a nitrogen atom. More preferably, only the ring skeleton constituting atom at the 3rd or 4th position is a nitrogen atom, for example, it is preferred that one or both of the ring skeleton constituting atoms at the 3rd and 4th positions are nitrogen atoms.
In the present invention, when the atomic group composed of a non-condensed heteroaromatic ring includes a triazine ring, the 2-position ring skeleton constituent atom in the nitrogen-containing aromatic group is preferably not a nitrogen atom.

  In the general formula (1), the number of heteroatoms in the non-condensed heteroaromatic ring of A is the same as or larger than the number of heteroatoms per one nitrogen-containing aromatic group of B. Here, when there are a plurality of nitrogen-containing aromatic groups of B, the number of heteroatoms per all nitrogen-containing aromatic groups satisfies the above condition. When the atomic group of A is composed of two or more non-fused heteroaromatic rings, the number of heteroatoms in the non-fused heteroaromatic ring of A represents the number of heteroatoms per one non-fused heteroaromatic ring. .

  In general formula (1), x and y each independently represents an integer of 1 or more. x is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3. 1 or 2 is particularly preferable. In addition, y is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, more preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. Further preferred.

  In the present invention, by using a heteroaromatic ring compound having a nitrogen-containing aromatic group having the above-described structure, a nitrogen-containing aromatic group is coordinated to an inorganic metal or a salt thereof to form a porous structure. When these compounds are further heated and heated, the central atomic group of the heteroaromatic ring compound is thermally decomposed to form an oxygen reduction reaction (ORR) active site, and a highly active nitrogen-containing carbon alloy can be obtained. . In the present invention, by constituting A in the general formula (1) from a 5- to 11-membered non-condensed heteroaromatic ring, the thermal decomposition of the non-condensed heteroaromatic part (central atomic group) can be easily advanced. . Thereby, formation of an oxygen reduction reaction (ORR) active site can be promoted, and a higher activity nitrogen-containing carbon alloy can be obtained.

  The coordination between the inorganic metal and the nitrogen-containing aromatic group is such that either one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the bonding position with L in the nitrogen-containing aromatic group are nitrogen atoms. In some cases, it becomes easier to proceed. This is because, when the ring skeleton constituent atom at the 2-position is a nitrogen atom, the distance between the hetero atom of the central atomic group and the nitrogen atom of the nitrogen-containing aromatic group is reduced, so that the inorganic metal is the central atomic group. This is thought to be due to coordination with a heteroatom to form a complex. Such coordination is not a preferred coordination mode of the inorganic metal and the nitrogen-containing aromatic group, and causes the thermal decomposition of the central atomic group to hardly proceed. For this reason, it is considered that when the ring skeleton constituent atom at the 2-position is a nitrogen atom, formation of an oxygen reduction reaction (ORR) active site is suppressed, and the catalytic activity of the nitrogen-containing carbon alloy is lowered.

  The heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is preferably represented by the following general formula (2).

In General Formula (2), Q ^{1 to} Q ³ each independently represents a hetero atom or a carbon atom, at least one of Q ^{1 to} Q ³ is a nitrogen atom, b1 to b3 are each independently a hydrogen atom, Represents a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of b1 to b3 is a substituted or unsubstituted nitrogen-containing aromatic group, In at least one, one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the binding site are nitrogen atoms. Q Number heteroatoms in non-fused heteroaromatic ring containing ¹ to Q ³ is or greater identical to the number of heteroatoms in the nitrogen-containing aromatic group per one of b1 to b3. Note that the binding site of b1 to b3, and b1 to b3, refers to the binding site of the linking group between the non-fused heteroaromatic ring containing Q ¹ to Q ^3.

In the general formula (2), Q ^{1 to} Q ³ each independently represent a hetero atom or a carbon atom, and at least one of Q ^{1 to} Q ³ represents a nitrogen atom. Q ^{1 to} Q ³ are each independently preferably a nitrogen atom, a sulfur atom, or a carbon atom, particularly preferably a nitrogen atom or a carbon atom, and any one is a nitrogen atom. Note that atoms in Q ^{1 to} Q ³ may be ionized. In the general formula (2), it is preferable that at least one is a nitrogen atom of Q ¹ to Q ^3, and more preferably all of Q ¹ to Q ³ is a nitrogen atom.

  B1-b3 in General formula (2) are synonymous with B in General formula (1), and its preferable range is also the same. In the general formula (2), b1 to b3 preferably represent a substituted or unsubstituted nitrogen-containing aromatic group, and b1 to b3 are preferably 5- or 6-membered rings, preferably 6-membered rings. Is more preferable. In addition, as a substituent which b1-b3 can take, in General formula (1), the substituent similar to the substituent which B can take can be illustrated.

  Furthermore, in the general formula (2), b1 to b3 are preferably a pyridyl group, a pyrimidyl group or a triazyl group, and more preferably a pyridyl group or a pyrimidyl group.

In at least one of the nitrogen-containing aromatic groups, either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms. In the present invention, when all of Q ^{1 to} Q ³ are nitrogen atoms, in b1 to b3, the ring skeleton constituting atom at the 2-position with respect to the binding site is preferably not a nitrogen atom. Note that when the ring skeleton constituting atom at position 2 in b1 is a nitrogen atom, Q ¹ and Q ³ are preferably carbon atoms, and when the atom at the 2nd position in b2 is nitrogen atom, Q ¹ And Q ² are preferably carbon atoms. When the ring skeleton constituting atom at the 2-position in b3 is a nitrogen atom, Q ² and Q ³ are preferably carbon atoms. That is, the distance between the nitrogen atom constituting the central atomic group and the nitrogen atom of the nitrogen-containing aromatic group represented by b1 to b3 is preferably a certain distance or more, and the distance between the nitrogen atoms of the nitrogen-containing aromatic group Is preferably 4 atoms or more.

In the general formula (2), the number of heteroatoms in the non-condensed heteroaromatic ring containing Q ^{1 to} Q ³ is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of b1 to b3. Here, when there are a plurality of nitrogen-containing aromatic groups b1 to b3, the number of heteroatoms per one nitrogen-containing aromatic group satisfies the above condition. When there are two or more non-fused heteroaromatic rings including Q ^{1 to} Q ³ , the number of heteroatoms in the non-fused heteroaromatic ring represents the number of heteroatoms per one non-fused heteroaromatic ring.

    The heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is preferably a compound represented by the following formula (3) or (4).

  The heteroaromatic ring compound having a nitrogen-containing aromatic group may be a compound represented by the following general formula (5).

  In general formula (5), A represents an atomic group composed of a 5- to 11-membered non-condensed heteroaromatic ring, L represents a single bond or a (x + 1) -valent linking group, B represents a hydrogen atom, substituted Or an unsubstituted aromatic group or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups In the above, any one or both of the ring skeleton constituting atoms at the 3rd and 4th positions relative to the bonding site with L are nitrogen atoms. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X represents an integer of 1 or more.

  A in the general formula (5) is the same as A in the general formula (1), and the preferred range is also the same. Moreover, L in General formula (5) is the same as L in General formula (1), and its preferable range is also the same.

  In the general formula (5), B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group Represents a group. Here, the nitrogen-containing aromatic group means a group having a nitrogen atom as a constituent atom of the aromatic group. B in the general formula (5) is the same as B in the general formula (1), and the preferred range is also the same. When a plurality of B are present, at least one of the Bs may be a substituted or unsubstituted nitrogen-containing aromatic group, but it is preferable that all Bs are substituted or unsubstituted nitrogen-containing aromatic groups. The nitrogen-containing aromatic group is preferably a pyridyl group, a pyrimidyl group, a triazyl group, or an imidazolyl group.

  When the aromatic group or nitrogen-containing aromatic group represented by B has a substituent, specific examples of preferred substituents can include the same examples as described above.

  In at least one of the substituted or unsubstituted nitrogen-containing aromatic groups represented by at least one B, one or both of the ring skeleton constituting atoms at the 3-position and 4-position with respect to the bonding site with L are nitrogen atoms. is there. In the substituted or unsubstituted nitrogen-containing aromatic group represented by at least one B, one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms. The preferred configuration is the same as B in the general formula (1).

  In the general formula (5), the number of heteroatoms in the non-condensed heteroaromatic ring of A is the same as or larger than the number of heteroatoms per one nitrogen-containing aromatic group of B. Here, when there are a plurality of nitrogen-containing aromatic groups of B, the number of heteroatoms per all nitrogen-containing aromatic groups satisfies the above condition.

  In the general formula (5), x represents an integer of 1 or more. x is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3. 1 or 2 is particularly preferable.

  Specific examples of the heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) include the following compounds. However, the present invention is not limited to the following specific examples.

  In addition, about the compound which has a benzene ring in central part, the nitrogen-containing aromatic group of a terminal part corresponds to the non-condensed heteroaromatic ring represented by A of General formula (1), and the connection part containing a benzene ring is common. It corresponds to the linking group represented by L in formula (1).

  As the heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1), among the above compounds, the following compounds are preferably used.

The above heteroaromatic ring compound having a nitrogen-containing aromatic group forms a crystal structure by two or more bonds or interactions selected from π-π interaction, coordination bond, charge transfer interaction and hydrogen bond. It is preferable. This is because by using a low molecular weight compound having a crystal structure, the intermolecular interaction can be improved and vaporization during firing when obtaining a nitrogen-containing carbon alloy can be suppressed.
The crystal structure here refers to the arrangement and arrangement of molecules in the crystal. In other words, the crystal structure consists of a repeating structure of unit cell, and the molecules are arranged at any position in the unit cell and oriented. In the crystal, the molecules have a uniform appearance. That is, since the arrangement of functional groups in the crystal is uniform, each molecular interaction is the same inside or outside the unit cell. For example, in the case of a heteroaromatic compound having a nitrogen-containing aromatic group having a laminated structure, an aromatic ring, a heterocyclic ring, a condensed polycyclic ring, a condensed heterocyclic polycyclic ring, an unsaturated group (nitrile group, vinyl group, allyl group, acetylene) Group) and the like (for example, an aromatic ring is face-to-face and has a π-π interaction (π-π stack)). Stacking is performed by SP ² orbits of carbons derived from unsaturated bonds in these rings and groups and regularly overlapping at equal intervals between molecules to form a stacked column structure.

  Further, in this stacked column structure, adjacent stacked columns have a uniform structure in which the intermolecular distance is defined by hydrogen bonding or van der Waals interaction. For this reason, it has the effect that the heat transfer in a crystal | crystallization is achieved easily.

  The heteroaromatic ring compound having a nitrogen-containing aromatic group used in the present invention preferably has crystallinity. The heteroaromatic ring compound having a nitrogen-containing aromatic group is preferable because the crystallinity is crystallinity, and the compound can be controlled in orientation during firing, so that it becomes a uniform carbon material.

  The heteroaromatic ring compound having a nitrogen-containing aromatic group preferably further has a melting point of 25 ° C. or higher. When the melting point is 25 ° C. or higher, there is an air layer that contributes to heat resistance during firing, boiling or bumping can be prevented from the relationship between temperature and vapor pressure, and a carbon material can be easily obtained.

The heteroaromatic ring compound having a nitrogen-containing aromatic group is not particularly limited to the molecular weight, but in the case of a low molecular weight compound or oligomer, it is preferably 60 to 2000, more preferably 100 to 1500, and 130 to 1000. It is particularly preferred that By setting it within the above range, purification before firing becomes easy.
When the heteroaromatic ring compound having a nitrogen-containing aromatic group is a polymer, the number average molecular weight is preferably 2,000 to 1,000,000, and more preferably 2,000 to 100,000. The molecular weight distribution (dispersion degree = weight average molecular weight / number average molecular weight) is not particularly limited, but is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. Since the electroconductivity of the carbon material obtained by setting it as the said range improves, it is preferable.
The measurement method of weight average molecular weight and number average molecular weight includes Japanese Industrial Standards (JIS K 7252 (how to determine the average molecular weight and molecular weight distribution of a polymer by plastic size exclusion chromatography), and size exclusion chromatography (SEC). The number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), the degree of dispersion (Mw / Mn), and the content of components having a molecular weight of less than 1,000 The rate can be determined.

The heteroaromatic ring compound having a nitrogen-containing aromatic group may be a polymer such as Poly (4-VinylPyridine), a low molecular compound or an oligomer in the above exemplary compounds. In the case of a polymer, the polymerization degree n is preferably 20 to 1.0 × 10 ⁴ , more preferably 20 to 1.0 × 10 ³ , and further preferably 20 to 1.0 × 10 ^2. preferable. In the case of a low molecular weight compound or oligomer, the polymerization degree n is preferably 2 to 20, and more preferably 4 to 10.
When the heteroaromatic ring compound having a nitrogen-containing aromatic group is a polymer, since the nitrogen-containing aromatic group is arranged by a covalent bond, by setting the polymerization degree within the above range, adjacent carbons are bonded at the time of firing. This is preferable because it is easy to perform and conductivity is improved.
When the heteroaromatic ring compound having a nitrogen-containing aromatic group is a low molecular weight compound or oligomer, the nitrogen-containing aromatic group is bonded by a covalent bond. The nitrogen aromatic group is preferred because it is oriented with the metal, the nitrogen-containing aromatic group is easily arranged, and vacancies are easily formed.

  In the present invention, the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably contained in an amount of more than 0.1% by mass, and 0.5 to 99% by mass with respect to the total mass in the precursor. Is more preferable, and it is further more preferable that 5-90 mass% is contained. By containing the heteroaromatic ring compound having a nitrogen-containing aromatic group within the above range, a carbon alloy having higher oxygen reduction activity can be generated.

  In addition, the hetero aromatic ring compound which has a nitrogen-containing aromatic group may be used independently, and 2 or more types may be mixed and used for it. Moreover, it is preferable that the metal content in the hetero aromatic ring compound which has nitrogen-containing aromatic groups other than the inorganic metal salt mentioned later is 10 ppm or less.

  The nitrogen content of the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably 0.1% by mass to 55% by mass, and preferably 1% by mass to 30% by mass with respect to the total mass of the precursor. Is more preferable, and it is particularly preferably 4% by mass to 20% by mass. By using a compound containing a nitrogen atom (N) within the above range, there is no need to introduce a separate nitrogen source compound, the nitrogen atom and metal are regularly positioned uniformly on the crystal edge, and the nitrogen and metal are It becomes easy to interact. Thereby, the composition ratio of nitrogen atom and metal can be a composition ratio having higher oxygen reduction activity.

The heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably a hardly volatile compound having a ΔTG of −95% to −0.1% at 400 ° C. in a nitrogen atmosphere, It is more preferably a hardly volatile compound of 1%, and particularly preferably -90% to -5%. The heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably a hardly volatile compound that is carbonized without being vaporized during firing.
Here, ΔTG is raised at 10 ° C./min from 30 ° C. to 1000 ° C. under a flow of 100 mL / min in TG-DTA measurement of a mixture of a heteroaromatic compound having a nitrogen-containing aromatic group and an inorganic metal salt. When heated, it refers to the mass reduction rate at 400 ° C. based on the mass at room temperature (30 ° C.).

The heteroaromatic ring compound having a nitrogen-containing aromatic group is also preferably a pigment having a structure represented by the general formula (1).
The pigment forms a stacked column structure by π-π interaction between molecules, and has a uniform structure in which the intermolecular distance is defined by hydrogen bonding or van der Waals interaction between the stacked columns. It has the effect that heat transfer is easily achieved. In addition, it has crystallinity, and is vibration-reduced and heat-resistant by phonon (quantized lattice vibration) against heat. Therefore, the decomposition temperature is maintained up to the carbonization temperature, and there is an effect that the vaporization of the decomposition product is reduced and the carbonization is achieved.
Among them, isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments or dyes obtained by converting the above pigments into A pigment such as a lake pigment pigmented with a metal ion is preferred, and a diketopyrrolopyrrole pigment, a quinacridone pigment, an isoindoline pigment, an isoindolinone pigment, a quinophthalone pigment, and a latent pigment obtained by laminating the above pigment ( (Described later) is more preferable. This is because, when these pigments are fired, the benzonitrile (Ph-CN) skeleton, which is decomposed and formed, becomes a reactive species, and a carbon alloy catalyst having higher oxygen reduction reaction activity is generated. Further, when the metal species (M) coexists, a complex of Ph—CN.

<Inorganic metal salt>
An inorganic metal salt is used for the preparation of the precursor described above. The inorganic metal salt is not particularly limited, but may be a hydroxide, oxide, nitride, sulfite, sulfide, sulfonate, carbonylate, nitrate, nitrite, halide or the like. Preferably, the counter ion is a halogen ion or a nitrate ion. It is preferable that the counter ion is a halide or nitrate in which a halogen ion, a nitrate ion or a sulfate ion is used, because the specific surface area can be increased by binding to carbon on the carbon surface generated during the thermal decomposition. In the present invention, the inorganic metal salt is preferably a halide, and particularly preferably an inorganic metal chloride.

  The inorganic metal salt can contain water of crystallization, and the inorganic metal salt is preferably a hydrated salt. Since the inorganic metal salt contains crystal water, the thermal conductivity is improved, which is preferable in that it can be uniformly fired. As the inorganic metal salt containing crystal water, for example, cobalt chloride (III) hydrate salt, iron chloride (III) hydrate salt, cobalt chloride (II) hydrate salt, iron chloride (II) hydrate salt is preferably used. it can.

  The metal species of the inorganic metal salt is preferably at least one of Fe, Co, Ni, Mn, and Cr, and more preferably Fe or Co. Fe, Co, Ni, Mn, and Cr salts are excellent in forming a nano-sized shell structure that improves the catalytic activity of the carbon catalyst, and in particular, Co and Fe form a nano-sized shell structure. It is preferable because it is particularly excellent. Moreover, Co and Fe contained in the carbon catalyst can improve the oxygen reduction activity of the catalyst in the carbon catalyst. Most preferably, it is Fe as a transition metal. The Fe-containing nitrogen-containing carbon alloy has a high rising potential, has a higher number of reaction electrons than Co, and can relatively improve the durability of the fuel cell. As long as the activity of the carbon catalyst is not inhibited, elements other than transition metals (for example, B, alkali metals (Na, K, Cs), alkaline earths (Mg, Ca, Ba), lead, tin, indium, thallium, etc. ) May be included in one or more types.

  In the present invention, the precursor includes the total of the heteroaromatic ring compound having a nitrogen-containing aromatic group and the inorganic metal salt contained in the precursor (however, the total includes the mass of hydrated water), It is preferable that the inorganic metal salt (however, the inorganic metal salt here includes the mass of hydrated water) exceeds 5 mass%. Thereby, the carbon alloy which has higher oxygen reduction activity can be produced | generated by interaction with a nitrogen atom. By firing an organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group, the heteroaromatic ring compound is decomposed, and the generated decomposition product forms a nitrogen-containing carbon alloy catalyst in the gas phase. At that time, if a metal is present in the vicinity of the gas phase, the decomposition product interacts with the metal (forms a complex), and the performance of the nitrogen-containing carbon alloy catalyst is further improved. Further, due to the catalytic action of a specific transition metal compound added to a heteroaromatic ring compound having a nitrogen-containing aromatic group containing a nitrogen atom (N) as a constituent element, the nitrogen atom (N) is increased on the carbon catalyst surface. It is preferable to form carbon fine particles containing a transition metal compound which forms a nitrogen-containing carbon alloy fixed at a concentration and interacts with the nitrogen atom (N). In addition, the transition metal compound which interacted with some nitrogen atoms (N) by the acid treatment mentioned later may drop off.

  The nitrogen-containing carbon alloy obtained in the present invention is based on the total of the heteroaromatic ring compound having a nitrogen-containing aromatic group and the inorganic metal salt contained in the precursor (however, the total includes the mass of hydrated water) In addition, it is preferable that the inorganic metal salt (however, the inorganic metal salt here includes the mass of hydrated water) exceeds 0.1% by mass, and exceeds 0.5% by mass and is 85% by mass or less. More preferably, it is contained more than 1 mass% and 70 mass% or less. By setting it within this range, a carbon alloy having high oxygen reduction reaction activity (ORR activity) can be generated.

The ORR activity can be measured as an ORR activity value by obtaining a potential by the method described in detail in Examples. To obtain high output, it is preferable the value of potential at the time of oxygen reduction is high, specifically, the potential of the current density values -1 mA / cm ² in the electrode coating weight of 0.05 mg / cm ² is 0 .39V or more is preferable, 0.43V or more is more preferable, and 0.45V or more is more preferable.
The potential of the current density values -1 mA / cm ² in the electrode coating amount of 0.5 mg / cm ² is preferably not less than 0.70 V, more preferably at least 0.72V, and even more preferably 0.74 V. The coating amount and the current density increase linearly, but as the coating amount increases, the current density decreases from the assumed straight line due to an increase in resistance between carbon alloy particles, an increase in diffusion resistance of oxygen and water, and the like. According to Ohm's law, the application amount and the potential are similarly deviated from linearity and become lower in the relationship between the application amount and the potential. The value of the potential at 0.5 mg / cm ² is a value that takes into account the catalytic activity and the conductivity of the carbon alloy shown at 0.05 mg / cm ² , and is particularly preferable because of its excellent conductivity.

  In the present invention, there is an advantage that the heteroaromatic ring compound having a nitrogen-containing aromatic group and the inorganic metal salt do not need to be uniformly dispersed in the organic material before firing. That is, when a heteroaromatic ring compound having a nitrogen-containing aromatic group undergoes calcination decomposition, if the decomposition product is in contact with a vaporized product such as an inorganic metal salt, an active species having oxygen reduction reaction activity is formed. Therefore, the oxygen reduction reaction activity of the carbon alloy is not affected by the mixed state of the heteroaromatic ring compound and the inorganic metal salt at room temperature.

  In addition, it is preferable that the particle diameter of inorganic metal salt is 0.001-100 micrometers in diameter. More preferably, it is 0.01-10 micrometers. By making the particle size of the inorganic metal salt within this range, it becomes possible to uniformly mix with the heteroaromatic ring compound having a nitrogen-containing aromatic group, and the heteroaromatic ring compound is likely to form a complex when it is decomposed. .

<Organic metal complex>
In the method for producing a nitrogen-containing carbon alloy of the present invention, the precursor preferably further contains at least one organometallic complex. By adding an organometallic complex to the precursor, in addition to obtaining high ORR activity, a carbon alloy catalyst having a high number of reaction electrons can be obtained.
Examples of organometallic complexes include compounds described in Basic Complex Engineering Study Group, Complex Chemistry-Fundamentals and Latest Topics, Kodansha Scientific (1994). A compound in which a ligand is coordinated can be preferably exemplified, and a metal acetate complex or a β-diketone metal complex can be preferably used. In addition, the organometallic complex can take the coordination number of various ligands, may be a coordination geometric isomer, and may have different valences of metal ions. The organometallic complex may be an organometallic compound having a metal-carbon bond.

Preferable metal ions are Fe, Co, Ni, Mn and Cr ions.
Preferred ligands include monodentate ligands (halide ion, cyanide ion, ammonia, pyridine (py), triphenylphosphine, carboxylic acid, etc.), bidentate ligands (ethylenediamine (en), β- Diketonate (acetylacetonate (acac), pivaloylmethane (DPM), diisobutoxymethane (DIBM), isobutoxypivaloylmethane (IBPM), tetramethyloctadione (TMOD)), trifluoroacetylacetonate (TFA), bipyridine (Bpy), phenanthrene (phen), etc.), multidentate ligands (ethylenediaminetetraacetate ion (edta), etc.).

Examples of the metal complex that can be used include the β-diketone metal complex (bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], tris (acetylacetonato) iron (III) [Fe ( acac) ₃ ], bis (acetylacetonato) cobalt (II) [Co (acac) ₂ ], tris (acetylacetonato) cobalt (III) [Co (acac) ₃ ], bis (dipivaloylmethane) iron (II) [Fe (DPM) ₂ ], tris (dipivaloylmethane) iron (III) [Fe (DPM) ₃ ], tris (dipivaloylmethane) cobalt (III) [Co (DPM) ₃ ] , bis (diisobutoxyphenyl methane) iron (II) [Fe (DIBM) 2], tris (diisobutoxyphenyl methane) iron (III) [Fe (DIBM) 3], tris (diisopropyl Tokishimetan) cobalt (III) [Co (DIBM) 3], bis (iso-butoxy pivaloyl methane) iron (II) [Fe (IBPM) 2], tris (isobutoxy pivaloyl methane) cobalt (III) [Co (IBPM) ₃ ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), tris (tetramethyloctadione) iron (III) [Fe (TMOD) ₃ ], tris (tetramethylocta Dione) cobalt (III) [Co (TMOD) ₃ ]), tris (1,10-phenanthrolinato) iron (III) chloride [Fe (phen) ₃ ] Cl ₂ , tris (1,10-phenant) Rorinato) cobalt (III) chloride _{[Co (phen) 3] Cl} 2, N, N'- ethylenediamine bis (salicylidene A Minato) iron (I ) [Fe (salen)], N, N′-ethylenediaminebis (salicylideneaminato) cobalt (II) [Co (salen)], tris (2,2′-bipyridine) iron (II) chloride [ Fe (bpy) ₃ ] Cl ₂ , tris (2,2′-bipyridine) cobalt (II) chloride [Co (bpy) ₃ ] Cl ₂ , iron phthalocyanine (MPc) and iron acetate [Fe (OAc) ₂ ] Can be mentioned.
Among them, β-diketone metal complexes (bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], tris (acetylacetonato) iron (III) [Fe (acac) ₃ ], bis (dipivaloyl) Methane) iron (II) [Fe (DPM) ₂ ], bis (diisobutoxymethane) iron (II) [Fe (DIBM) ₂ ], bis (isobutoxypivaloylmethane) iron (II) [Fe (IBPM) ₂ ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], tris (2,2′-bipyridine) iron (II) chloride [Fe (bpy) ₃ ] Cl ₂ , iron phthalocyanine (MPc) or iron acetate [Fe (OAc) ₂ ] is preferred, and acetylacetone iron (II The complex bis (acetylacetonato) iron (II) [Fe (acac) ₂ ] is preferably used.

(Β-diketone metal complex)
The organometallic complex preferably includes a β-diketone metal complex. As the organometallic complex, a β-diketone metal complex may be used alone, or a β-diketone metal complex and another organometallic complex may be mixed and used. The β-diketone metal complex represents a compound represented by the following general formula (6) and a tautomer thereof.

In the general formula (6), M represents a metal, R ¹ and R ³ each independently represents a hydrocarbon group which may have a substituent, and R ² has a hydrogen atom or a substituent. The hydrocarbon group which may be carried out is shown. R ¹ , R ² and R ³ may be bonded to each other to form a ring. n represents an integer of 0 or more, and m represents an integer of 1 or more. In this compound, β-diketone or its ion is coordinated or bonded to the atom or ion of metal M.

  Preferred metals include Fe, Co, Ni, Mn and Cr, more preferably Fe and Co, and still more preferably Fe.

Examples of the “hydrocarbon group” in the hydrocarbon group optionally having a substituent for R ¹ , R ² , and R ³ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , Heterocyclic (heterocyclic) hydrocarbon groups, and groups in which a plurality of these are bonded. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups (C _1-6 alkyl groups and the like); An alkenyl group ( _C2-6 alkenyl group etc.) etc. are mentioned. Examples of alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl and cyclohexyl groups (3 to 15 membered cycloalkyl groups); cycloalkenyl groups such as cyclohexenyl groups (3 to 15 membered cycloalkenyl groups and the like) ); A bridged carbocyclic group such as an adamantyl group (such as a bridged carbocyclic group having about 6 to 20 carbon atoms). Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group (aryl group) having about 6 to 20 carbon atoms such as a phenyl group and a naphthyl group. As the heterocyclic (heterocyclic) hydrocarbon group, for example, a nitrogen-containing five-membered hydrocarbon group such as a pyrrolyl group, an imidazolyl group or a pyrazolyl group; Member ring hydrocarbon group; pyrrolidinyl group, indolizinyl group, isoindolyl group, isoinindolinyl group, indolyl group, indazolyl group, purinyl group, quinolidinyl group, quinolinyl group, naphthyridinyl group, phthalazinyl group, quinoxalinyl group, cinnolinyl group, pteridinyl group Nitrogen-containing condensed bicyclic hydrocarbon groups such as carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, and antiridinyl group Hydrocarbon group; oxygen-containing monocyclic system, oxygen-containing polycyclic system Sulfur-containing and selenium-containing tellurium ring system hydrocarbon group.

Examples of the substituent that the hydrocarbon group may have include, for example, a halogen atom such as fluorine, chlorine and bromine; an alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy, and t-butyloxy group (C _1-4 alkoxy group etc.); hydroxy group; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups (C _1-4 alkoxy-carbonyl group etc.); acyl groups such as acetyl, propionyl and benzoyl groups (C _{1- 10} acyl group); cyano group; nitro group and the like.

Examples of the ring formed by combining R ¹ , R ² , and R ³ with each other include, for example, a 5- to 15-membered cycloalkane ring or cycloalkene ring such as a cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, etc. Is mentioned.

R ¹ and R ³ include an alkyl group (C _1-6 alkyl group etc.), an alkenyl group (C _2-6 alkenyl group etc.), a cycloalkyl group (3-15 membered cycloalkyl group etc.), a cycloalkenyl group. (3- to 15-membered cycloalkenyl group etc.), aryl group (C _6-15 aryl group etc.), aryl group having a substituent (C ₆ having a substituent such as p-methylphenyl group, p-hydroxyphenyl group) _-15 aryl group). R ² includes a hydrogen atom, an alkyl group (C _1-6 alkyl group etc.), an alkenyl group (C _2-6 alkenyl group etc.), a cycloalkyl group (3-15 membered cycloalkyl group etc.), a cycloalkenyl group. (3- to 15-membered cycloalkenyl group etc.), aryl group (C _6-15 aryl group etc.), aryl group having a substituent (C ₆ having a substituent such as p-methylphenyl group, p-hydroxyphenyl group) _-15 aryl group).

In the compound represented by the general formula (6), the valence n of the metal may be any of 0, 1, 2, 3 and the like, but is usually divalent or trivalent. When the metal is divalent or trivalent, the β-diketone is coordinated as the corresponding anion, β-diketonate. When the metal valence is n, the coordination number m is usually the same. However, a solvent or the like may be axially coordinated with the metal. In that case, the valence n and the coordination number m of the metal may be different.
Examples of the solvent that may be axially coordinated include pyridine, acetonitrile, alcohol, and the like, but any solvent that can be axially coordinated may be used.

  As the β-diketone iron complex, a commercially available product may be used as it is or after purification, or it may be prepared and used. It can also be generated and used in a reaction system. When it is generated in the reaction system, for example, iron chloride, hydroxide and β-diketone such as acetylacetone may be added. At this time, a base such as ammonia, amines, alkali metal or alkaline earth metal hydroxides, carbonates or carboxylates can be added as necessary.

  The addition amount of β-diketone iron complex is usually 0.001 to 50 mol%, preferably 0.01 to 20 mol%, particularly preferably about 0.1 to 10 mol%.

(Conductive aid)
In the present invention, a conductive additive may be added to the precursor and baked, or may be added to the carbon alloy. Since the conductive auxiliary agent is uniformly dispersed, it is preferable to add a conductive auxiliary agent and fire.

  Although it does not specifically limit as a conductive support agent, For example, Norrit (made by NORIT), Ketjen black (made by Lion), Vulcan (made by Cabot), black pearl (made by Cabot), acetylene black (Chevron) Carbon black such as (manufactured) (all are trade names), graphite, and carbon materials such as fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.

  The addition rate of the conductive assistant is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 20% by mass, and 1% by mass with respect to the total mass of the precursor. More preferably, the content is from 10% to 10% by mass. If too much conductive additive is added, the aggregation / growth of the metal produced from the inorganic metal salt in the system becomes non-uniform and the desired porous nitrogen-containing carbon cannot be obtained, which is not suitable.

<Method for producing nitrogen-containing carbon alloy>
In the method for producing a nitrogen-containing carbon alloy of the present invention, the step of firing the precursor is as follows:
(1) A step of preparing a precursor by mixing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt containing one or more of Fe, Co, Ni, Mn and Cr;
(2) a temperature raising step for raising the temperature of the precursor from 1 to 2000 ° C. per minute from room temperature to the carbonization temperature under an inert atmosphere;
(3) a carbonization step of holding at 400 to 2000 ° C. for 0.1 to 100 hours;
(4) It is preferable to include a cooling step of cooling from the carbonization temperature to room temperature.
In the step of firing the precursor,
(5) After the carbonization treatment, the carbon alloy may be cooled to room temperature and then pulverized.
Furthermore, the manufacturing method of the nitrogen-containing carbon alloy of the present invention is the firing step,
(6) It preferably includes a step of washing the baked nitrogen-containing carbon alloy with an acid,
(7) More preferably, after the acid cleaning step, a step of refiring the acid-cleaned nitrogen-containing carbon alloy is included.
Hereinafter, the above-described steps (1) to (7) will be described in order for the method for producing a nitrogen-containing carbon alloy of the present invention.

(1) Precursor preparation step In the precursor preparation step, the above-described heteroaromatic ring compound having a nitrogen-containing aromatic group and the above-described inorganic metal salt are mixed to prepare a precursor.

Although the precursor adjusted in the manufacturing process of a nitrogen-containing carbon alloy is baked after that, it is preferable to further include the process of grind | pulverizing a precursor before a baking process.

(2) Temperature raising step, (3) Carbonization step, and (4) Cooling step The production method of the present invention includes a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure and an inorganic metal salt. It is preferable that the precursor is heated to the carbonization temperature and cooled to room temperature after the heat treatment.

Further, the temperature may be raised in multiple stages in the temperature raising process of the temperature raising process and the re-baking process described later.
Of the multi-stage temperature raising processes, the latter stage of the temperature raising process may be carried out by holding the temperature after the completion of the preceding temperature raising process or by raising the temperature as it is. Alternatively, after cooling to room temperature, the temperature may be raised and a subsequent temperature increase process may be performed.
Moreover, when it cools to room temperature after the temperature rising process of a front | former stage, the sample after a process may be grind | pulverized uniformly by the below-mentioned (5) grinding | pulverization process, and you may shape | mold further. Alternatively, the metal may be removed by acid cleaning of the sample after the treatment in (6) acid cleaning step described later.

In the temperature raising process, the sample before treatment may be inserted into a carbonization device and then heated from room temperature to a predetermined temperature, or may be increased by inserting the sample before treatment into a carbonization device or the like at a predetermined temperature. May be warm.
Preferably, the temperature of the sample before processing is raised from room temperature to a predetermined temperature. When raising the temperature to a predetermined temperature, it is preferable to keep the temperature raising rate constant. More specifically, the rate of temperature increase is preferably 1 to 2000 ° C./min, more preferably 1 to 1000 ° C./min, and 1 to 500 ° C./min. Is more preferable.

(Preliminary carbide)
In order to obtain a preliminary carbide having pores, it is preferable to perform the previous treatment of the organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt at a relatively low temperature. In such a low temperature treatment, a constant temperature may be maintained. By doing so, only a heat-stable structure can be maintained, and unstable impurity components, solvents, and the like can be removed.

  In the temperature raising treatment performed at a relatively low temperature, it is preferable to raise the temperature of an organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt to 100 ° C to 1500 ° C, and 150 ° C to 1050 ° C. It is more preferable to raise the temperature to 200 ° C to 1000 ° C. By doing so, a uniform preliminary carbide is obtained.

  It is preferable to perform said temperature rising process in inert atmosphere. The inert atmosphere refers to a gas atmosphere such as a nitrogen gas or a rare gas atmosphere. Note that even if oxygen is contained, the atmosphere may be any atmosphere in which the amount of oxygen is limited to such an extent that the workpiece is not burned. The inert atmosphere may be either a closed system or a distribution system that distributes a new gas, and is preferably a distribution system. In the case of a circulation system, the gas flow rate is preferably 0.01 to 2.0 liters / minute per 36 mmφ inner diameter, and the gas flow rate is 0.05 to 1.0 per 36 mmφ inner diameter. It is more preferable to circulate a gas of 1 liter / min, and it is particularly preferable that the gas flow rate is 0.1 to 0.5 liter / min of gas per an inner diameter of 36 mmφ.

  After the temperature raising treatment, the temperature holding time is 0.1 to 100 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 5 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.

  The heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.

(Infusible)
In the heat treatment up to the carbonization temperature, the portions of the temperature rise treatment are collectively referred to as an infusible treatment.
In order to obtain an infusible material, the subsequent temperature increase treatment is continued following the temperature increase treatment of the precursor containing the heteroaromatic ring compound having a nitrogen-containing aromatic group having the specific structure in the previous stage and the inorganic metal salt. It is preferable to do so. As a result, the residual heat of the previous stage can be utilized, the decomposition reaction and the carbonization reaction of the organic material can be continuously performed, and the decomposition product and the metal interact with each other, so that the metal is more active. It can be stabilized with. In addition, it is preferable to use what contains an iron ion in a bivalent state as a metal. As a result, a carbon alloy having high oxygen reduction performance can be produced.

  The subsequent temperature increase treatment is preferably performed in an inert atmosphere, and the inert atmosphere may be either a closed system or a distribution system for circulating a new gas, and is preferably a distribution system. In the case of a circulation system, the gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mmφ inside diameter, and the gas flow rate is 0.02 to 1 per 36 mmφ inside diameter. More preferably, a gas of 0.0 liter / min is circulated, and the flow rate of the gas is particularly preferably 0.05 to 0.5 liter / min. The downstream gas flow rate may be different from the upstream gas flow rate.

  After the temperature raising treatment, the temperature holding time is 0.1 to 100 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 5 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.

  The heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.

(carbide)
In order to obtain a carbide, it is preferable to cool to room temperature after the temperature rising treatment in the previous stage, uniformly pulverize, perform acid cleaning, and then perform the temperature rising process in the subsequent stage. By doing so, it is possible to raise the treatment temperature in the carbonization treatment, and to obtain a carbon alloy having a more regular carbon structure. As a result, the conductivity of the carbon alloy is improved, high oxygen reduction performance is obtained, and durability as a catalyst is also improved.
It is also preferable to perform carbonization treatment at a high temperature directly from the previous stage. By doing so, the yield of the carbon alloy may be reduced, but the crystallite size of the obtained carbon alloy is uniform, so that the metal is uniformly distributed and the state of high activity is maintained. As a result, it becomes possible to produce a carbon alloy having excellent oxygen reduction performance. In addition, it is preferable that such process temperature does not exceed carbonization temperature, and an appropriate carbon alloy can be obtained by performing carbonization process in such a temperature range.

The firing temperature of the carbonization treatment of the precursor containing a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure and an inorganic metal salt is the same as that of the heteroaromatic ring compound having a nitrogen-containing aromatic group. The upper limit of the carbonization temperature needs to be 2000 ° C., although it is not particularly limited as long as it is a temperature to be converted.
In the case of a precursor containing an inorganic metal salt, the lower limit of the reaction temperature is preferably 400 ° C, more preferably 500 ° C, even more preferably 600 ° C, and even more preferably 700 ° C. . By setting the reaction temperature within the above range, carbon alloy having high catalytic performance due to advanced carbonization can be obtained. Moreover, if reaction temperature is 2000 degrees C or less, nitrogen will remain in carbon skeleton and it can be set as desired N / C atomic ratio, and sufficient oxygen reduction reaction activity will be obtained.
The firing temperature is preferably 700 to 1200 ° C, particularly preferably 700 to 1000 ° C. When carbonization treatment is performed within this range, the yield of carbon alloy may be reduced, but the crystallite size of the obtained carbon alloy is uniform, so that the metal is uniformly distributed and the state of high activity is maintained. The As a result, it becomes possible to produce a carbon alloy having excellent oxygen reduction performance. Further, by performing the carbonization treatment within the above range, nitrogen easily remains in the carbon skeleton due to the action of the generated inorganic metal, and the oxygen reduction reaction activity can be enhanced.

  The temperature raising treatment is preferably performed under a flow of an inert gas or a non-oxidizing gas, and such an atmosphere may be either a closed system or a flow system for flowing a new gas, preferably a flow system. It is. In the case of a flow system, the gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mmφ inner diameter, and 0.02 to 1.0 liter / min per 36 mmφ inner diameter. Is more preferable, and it is particularly preferable to circulate a gas of 0.05 milliliter to 0.5 liter / min per 36 mmφ inside diameter. It is preferable for the flow rate to be within this range because the desired nitrogen-containing carbon alloy can be suitably obtained.

  The treatment time of the carbonization treatment is 0.1 hour to 100 hours, preferably 0.2 hours to 10 hours, and more preferably 0.5 hours to 5 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.

  The heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.

(5) Crushing treatment After the carbonization treatment, the carbon alloy may be cooled to room temperature and then crushed. The pulverization treatment can be performed by any method known to those skilled in the art, and for example, pulverization can be performed using a ball mill, agate pulverization, mechanical pulverization, or the like.

(6) Acid Washing Process The method for producing a nitrogen-containing carbon alloy of the present invention may include an acid washing process for washing the fired nitrogen-containing carbon alloy with an acid after the firing process. The ORR activity can be improved by acid cleaning of the metal on the surface of the produced carbon alloy catalyst. Without being bound by any theory, it is expected that a porous nitrogen-containing carbon alloy having optimum porosity can be obtained by this acid cleaning treatment.
In the acid cleaning treatment, any aqueous Bronsted (proton) acid including a strong acid or a weak acid having a pH of 7 or less can be used in the acid cleaning step. Furthermore, an inorganic acid (mineral acid) or an organic acid can be used. Examples of suitable acids include HCI, HBr, HI, H ₂ SO ₄ , H ₂ SO ₃ , HNO ₃ , HClO ₄ , [HSO ₄ ] ⁻ , [HSO ₃ ] ⁻ , [H ₃ O] ⁺ , H ₂ [C ₂ O ₄ ], HCO ₂ H, HCIO ₃ , HBrO ₃ , HBrO ₄ , HIO ₃ , HIO ₄ , FSO ₃ H, CF ₃ SO ₃ H, CF ₃ CO ₂ H, CH ₃ CO ₂ H, B (OH) ₃ , etc. (including any combination thereof), but are not limited to these. In addition, the method described in JP-T-2010-524195 can also be used in the present invention.

(7) Re-baking process It is preferable that the manufacturing method of the nitrogen-containing carbon alloy of this invention further includes the process of grind | pulverizing the baked nitrogen-containing carbon alloy, and the process of re-baking after a baking process. More preferably, after the acid cleaning step, a step of refiring the acid-cleaned nitrogen-containing carbon alloy is included. By such a refiring step, the potential can be improved with an increase in the coating amount when the nitrogen-containing carbon alloy is applied to the electrode, and the ORR activity can be improved.

  Since the refiring process needs to be performed at a temperature higher than the calcining process for the purpose of promoting graphitization of carbon, the calcining temperature in the refiring process is preferably 500 to 2000 ° C, and preferably 600 to 1500 ° C. Is more preferable, and it is still more preferable that it is 1000-1500 degreeC.

From the viewpoint of promoting graphitization of carbon while maintaining a high content ratio of nitrogen atoms in the carbon alloy during firing, firing may be performed in a pressurized state during the reaction. The gas discharge port may be trapped with water and fired in a state where back pressure is applied.
The pressure in the carbonization step is 0.01 to 5 MPa, preferably 0.05 to 1 MPa, more preferably 0.08 to 0.3 MPa, and particularly preferably 0.09 to 0.15 MPa. High-pressure treatment is not preferable because it has a diamond structure constituted by sp ³ orbitals.

  The method of the refiring step is not particularly limited, but preferably a tubular furnace, a rotary furnace (rotary kiln), a roller hearth kiln, a pusher kiln, a multi-stage furnace, a vacuum gas replacement furnace, a tunnel furnace, a fluidized firing furnace, and the like are more preferable. Uses a rotary furnace (rotary kiln), a vacuum gas replacement furnace, a vacuum gas replacement rotary furnace (rotary kiln), a tunnel furnace, and a fluidized firing furnace, and particularly preferably a vacuum gas replacement rotary furnace (vacuum gas replacement rotary kiln).

It is preferable to further include a step of deaeration and nitrogen substitution before the step of refiring. By providing such a process, the oxygen concentration can be reduced. In the step of deaeration and nitrogen replacement, it is preferable to perform nitrogen gas replacement after deaeration with a vacuum pump. In particular, it is preferable to repeat the operation of replacing nitrogen gas multiple times after deaeration with a vacuum pump. At this time, the apparatus used for deaeration is not particularly limited as long as it can be deaerated, but it is preferable to use a vacuum gas replacement furnace or a vacuum gas replacement rotary furnace (rotary kiln). The pressure during vacuum degassing is not particularly limited, but is preferably 4 × 10 ⁴ Pa or less, more preferably 4 × 10 ³ Pa or less, and particularly preferably 2 × 10 ² Pa or less.

When the carbon alloy is refired, it is preferable to flow the carbon alloy in order to make the performance of the carbon alloy uniform. The apparatus used at this time is not particularly limited as long as it can flow the carbon alloy, but it is preferable to use a rotary furnace (rotary kiln), a vacuum gas replacement rotary furnace (rotary kiln), or a fluidized firing furnace.
In the case of using a rotary furnace (rotary kiln) or a vacuum gas replacement rotary furnace (rotary kiln), the sample tube is rotated at the time of firing, but is not limited to the rotational speed, speed change, and the like. The rotation speed is preferably 10 rpm or less, more preferably 5 rpm or less.

In the method for producing a nitrogen-containing carbon alloy of the present invention, it is preferable to perform a carbonization treatment in the presence of an activator (activation step). By carbonizing at high temperature in the presence of an activator, the pores of the carbon alloy develop and the surface area increases, and the exposure of the metal on the surface of the carbon alloy improves, thereby improving the performance as a catalyst. To do. The surface area of the carbide can be measured by the N ₂ adsorption amount.

The activator that can be used is not particularly limited. For example, carbon dioxide, ammonia gas, water vapor, air, oxygen gas, hydrogen gas, carbon monoxide gas, methane gas, alkali metal hydroxide, zinc chloride, and phosphoric acid. At least one selected from the group consisting of carbon dioxide, ammonia gas, water vapor, air, and oxygen gas can be used, more preferably at least one selected from the group consisting of:
The gas activator is preferably diluted with an inert gas. Examples of the inert gas to be diluted include nitrogen gas and rare gases (for example, argon gas, helium gas, and neon gas).
The gas activator may be contained in an atmosphere of carbonization treatment in an amount of 2 to 80 mol%, preferably 10 to 60 mol%. If it is 2 mol% or more, a sufficient activation effect can be obtained, while if it exceeds 80 mol%, the activation effect becomes remarkable and the yield of carbide is remarkably reduced, making it impossible to produce carbide efficiently. There is a fear. In addition, the solid activator such as alkali metal hydroxide may be mixed with the carbonized substance in a solid state, or after being dissolved or diluted with a solvent such as water, impregnated with the carbonized substance or in a slurry state. And may be kneaded into the article to be carbonized. The liquid activator may be diluted with water or the like and then impregnated with the carbonized material or kneaded into the carbonized material.
During the heat treatment, the pressure in the gas phase may be any of normal pressure, pressurization, and reduced pressure, but is preferably pressurized at a high temperature.
The gas may be stationary or distributed, but is preferably distributed from the viewpoint of discharging generated impurities.

  Nitrogen atoms can also be introduced after carbonization. At this time, as a method for introducing nitrogen atoms, a liquid phase doping method, a gas phase doping method, or a gas phase-liquid phase doping method can be used. For example, the carbon alloy can be heat-treated by holding it at 200 to 1200 ° C. for 5 to 180 minutes in an ammonia atmosphere as a nitrogen source to introduce nitrogen atoms onto the surface of the carbon catalyst.

[Nitrogen-containing carbon alloy]
The nitrogen-containing carbon alloy of the present invention is produced by the above-described method for producing a nitrogen-containing carbon alloy.

The nitrogen-containing carbon alloy of the present invention obtained by firing the precursor is a nitrogen-containing carbon alloy into which nitrogen has been introduced. The nitrogen-containing carbon alloy of the present invention preferably contains graphene, which is an aggregate of carbon atoms having a hexagonal network structure in which carbon is chemically bonded by sp ² hybrid orbitals and spreads in two dimensions.

  Furthermore, in the nitrogen-containing carbon alloy of the present invention, the content of surface nitrogen atoms in the carbon catalyst is more preferably 0.02 to 0.3 in terms of atomic ratio (N / C) to the surface carbon. When the atomic ratio (N / C) of the nitrogen atom to the carbon atom is less than 0.02, the number of effective nitrogen atoms bonded to the metal is reduced, and sufficient oxygen reduction catalyst characteristics cannot be obtained. Moreover, when the atomic ratio (N / C) of nitrogen atoms to carbon atoms exceeds 0.3, the strength of the carbon skeleton of the carbon alloy is lowered, and the electrical conductivity is lowered.

  Further, the skeleton of the carbon alloy only needs to be formed of at least carbon atoms and nitrogen atoms, and may contain hydrogen atoms, oxygen atoms, and the like as other atoms. In that case, the atomic ratio ((other atoms) / (C + N)) of other atoms to carbon atoms and nitrogen atoms is preferably 0.3 or less.

In specific surface area analysis, carbon alloy is put in a predetermined container, cooled to liquid nitrogen temperature (-196 ° C), nitrogen gas is introduced into the container and adsorbed, and the adsorption amount of single molecules and adsorption parameters are determined from the adsorption isotherm And the BET (Brunauer-Emmett-Teller) method for calculating and calculating the specific surface area of the sample from the molecular occupation cross section (0.162 cm ² ) of nitrogen.

  The pore shape of the carbon alloy is not particularly limited, and for example, pores may be formed only on the surface, or pores may be formed not only on the surface but also inside. When pores are also formed inside, for example, it may be tunnel-shaped, and it has a shape in which polygonal cavities such as spherical or hexagonal columns are connected to each other. It may be.

The specific surface area of the carbon alloy is preferably at 90m ² / g or more, more preferably 350 meters ² / g or more, and particularly preferably 670m ² / g or more. However, when the catalytically active site (metal coordination product or configuration space (field) having at least C, N, and metal ions as constituents) is generated and formed at a high density, it may be outside the above range.
From the viewpoint of sufficient oxygen reaching the depth of the pores and obtaining sufficient oxygen reduction catalyst characteristics, the specific surface area of the carbon alloy is preferably 3000 m ² / g or less, and preferably 2000 m ² / g or less. More preferred is 1500 m ² / g or less.

  The shape of the nitrogen-containing carbon alloy of the present invention is not particularly limited as long as it has oxygen reduction reaction activity. For example, a large distorted structure such as a sheet shape, a fiber shape, a plate shape, a column shape, a block shape, a particle shape, many ellipses other than a spherical shape, a flat shape, a square shape, and the like can be given. From the viewpoint of easy dispersion, it is preferably a block shape or a particle shape. However, when a slurry described later is applied and dried, it is preferably a fiber shape, a plate shape, or a column shape from the viewpoint of imparting thixotropy.

Furthermore, the slurry containing a carbon alloy can be produced by dispersing the nitrogen-containing carbon alloy of the present invention in a solvent. Thus, for example, when preparing an electrode catalyst for a fuel cell or an electrode material for a power storage device, a slurry in which a carbon alloy is dispersed in a solvent is applied to a support material, baked, and dried, so that an arbitrary shape is obtained. It is possible to form a carbon catalyst that has been processed into Thus, by making a carbon alloy into a slurry, the workability of the carbon catalyst is improved and it can be easily used as an electrode catalyst or an electrode material.
Fuel cell carbon alloy catalyst of the present invention preferably has a coating amount after drying of the nitrogen-containing carbon alloy is 0.01 mg / cm ² or more, more preferably 0.02~100mg / cm ^2, Particularly preferred is 0.05 to 10 mg / cm ² .
As the solvent, a solvent used when producing an electrode catalyst for a fuel cell or an electrode material for a power storage device can be appropriately selected and used. For example, as a solvent used when producing an electrode material for a power storage device, diethyl carbonate (DEC), dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), ethylene carbonate (EC), ethyl methyl carbonate (EMC) ), N-methyl-2-pyrrolidone (NMP), propylene carbonate (PC), γ-butyrolactone (GBL), etc., can be used alone or in combination. In addition, examples of the solvent used in preparing the fuel cell electrode catalyst include water, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, methyl ethyl ketone, and acetone.

<Application of nitrogen-containing carbon alloy>
The use of the nitrogen-containing carbon alloy of the present invention is not particularly limited to structural materials, electrode materials, filtration materials, catalyst materials, etc., but is preferably used as electrode materials for power storage devices such as capacitors and lithium secondary batteries. More preferably, it is used as a carbon catalyst for a fuel cell, zinc-air battery, lithium-air battery or the like having reactive activity. In the electrode membrane assembly including the solid polymer electrolyte membrane and the catalyst layer provided in contact with the solid polymer electrolyte membrane, the catalyst may be included in the catalyst layer. Furthermore, the electrode membrane assembly can be provided in a fuel cell.

(Fuel cell)
FIG. 1 shows a schematic configuration diagram of a fuel cell 10 using a carbon catalyst made of a nitrogen-containing carbon alloy of the present invention. The carbon catalyst is applied to the anode electrode and the cathode electrode.
The fuel cell 10 includes a separator 12, an anode electrode catalyst (fuel electrode) 13, a cathode electrode catalyst (oxidant electrode) 15, and a separator 16 that are disposed so as to sandwich the solid polymer electrolyte 14. As the solid polymer electrolyte 14, a fluorine-based cation exchange resin membrane represented by a perfluorosulfonic acid resin membrane is used. Moreover, the fuel cell 10 provided with the carbon catalyst in the anode electrode catalyst 13 and the cathode electrode catalyst 15 is configured by bringing the carbon catalyst into contact with both of the solid polymer electrolyte 14 as the anode electrode catalyst 13 and the cathode electrode catalyst 15. The By forming the carbon catalyst described above on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 13 and the cathode electrode catalyst 15 to both main surfaces of the solid polymer electrolyte 14 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).

  In a conventional fuel cell, a gas diffusion layer made of a porous sheet (for example, carbon paper) that also functions as a current collector is interposed between the separator and the anode and cathode electrode catalyst. In contrast, in the fuel cell 10 of FIG. 1, a carbon catalyst having a large specific surface area and high gas diffusibility can be used as the anode and cathode electrode catalyst. By using the above-mentioned carbon catalyst as an electrode, even when there is no gas diffusion layer, the carbon catalyst has a gas diffusion layer function, and the anode and cathode electrode catalysts 13, 15 and the gas diffusion layer are integrated. Since the battery can be configured, the fuel cell can be reduced in size and the cost can be reduced by omitting the gas diffusion layer.

The separators 12 and 16 support the anode and cathode electrode catalyst layers 13 and 15 and supply and discharge reaction gases such as fuel gas H ₂ and oxidant gas O ₂ . When a reaction gas is supplied to each of the anode and cathode electrode catalysts 13 and 15, a gas phase (reaction gas) and a liquid phase (solid) are formed at the boundary between the carbon catalyst provided on both electrodes and the solid polymer electrolyte 14. A three-phase interface of a polymer electrolyte membrane) and a solid phase (a catalyst possessed by both electrodes) is formed. And direct-current power generate | occur | produces by producing an electrochemical reaction.
In the above electrochemical reaction,
Cathode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
Anode side: H ₂ → 2H ⁺ + 2e ⁻
The H ⁺ ions generated on the anode side move toward the cathode side in the solid polymer electrolyte 14, and e ⁻ (electrons) move to the cathode side through an external load. On the other hand, on the cathode side, oxygen contained in the oxidant gas reacts with H ⁺ ions and e ⁻ that have moved from the anode side to generate water. As a result, the above-described fuel cell generates direct-current power from hydrogen and oxygen to generate water.

(Power storage device)
Next, a power storage device in which the carbon catalyst made of the nitrogen-containing carbon alloy of the present invention is applied to an electrode material will be described. FIG. 2 shows a schematic configuration diagram of an electric double layer capacitor 20 using a carbon catalyst made of nitrogen-containing carbon alloy and having an excellent storage capacity.
In the electric double layer capacitor 20 shown in FIG. 2, the first electrode 21 and the second electrode 22 which are polarizable electrodes are opposed to each other through the separator 23, and are accommodated in the outer lid 24a and the outer case 24b. ing. The first electrode 21 and the second electrode 22 are connected to the exterior lid 24a and the exterior case 24b via current collectors 25, respectively. The separator 23 is impregnated with an electrolytic solution. The electric double layer capacitor 20 is configured by caulking and sealing the outer lid 24a and the outer case 24b while being electrically insulated via the gasket 26.

  In the electric double layer capacitor 20 of FIG. 2, the carbon catalyst made of the above-described nitrogen-containing carbon alloy can be applied to the first electrode 21 and the second electrode 22. And the electric double layer capacitor by which the carbon catalyst was applied to the electrode material can be comprised. The above-described carbon catalyst has a fibrous structure in which nanoshell carbon is aggregated, and furthermore, since the fiber diameter is in a nanometer unit, the specific surface area is large, and the electrode interface where charges are accumulated in the capacitor is large. Furthermore, the above-mentioned carbon catalyst is electrochemically inactive with respect to the electrolytic solution, and has appropriate electrical conductivity. For this reason, the electrostatic capacitance per unit volume of an electrode can be improved by applying as an electrode of a capacitor.

  Similarly to the above-described capacitor, for example, the above-described carbon catalyst can be applied as an electrode material composed of a carbon material, such as a negative electrode material of a lithium ion secondary battery. And since the specific surface area of a carbon catalyst is large, a secondary battery with a large electrical storage capacity can be comprised.

(Environmental catalyst)
Next, an example in which the nitrogen-containing carbon alloy of the present invention is used as a substitute for an environmental catalyst containing a noble metal such as platinum will be described.
As a catalyst for exhaust gas purification for removing pollutants contained in polluted air (mainly gaseous substances) etc. by decomposition treatment, a catalyst material composed of noble metal materials such as platinum alone or in combination Environmental catalysts are used. The above-mentioned carbon catalyst can be used as an alternative to these exhaust gas purifying catalysts containing noble metals such as platinum. Since the above-described carbon catalyst is provided with an oxygen reduction reaction catalytic action, it has a function of decomposing substances to be treated such as pollutants. For this reason, since it is not necessary to use expensive noble metals, such as platinum, by comprising an environmental catalyst using the above-mentioned carbon catalyst, a low-cost environmental catalyst can be provided. Further, since the specific surface area is large, the treatment area for decomposing the material to be treated per unit volume can be increased, and an environmental catalyst having an excellent decomposition function per unit volume can be constituted.
By using the above-mentioned carbon catalyst as a carrier, a noble metal-based material such as platinum used in conventional environmental catalysts is carried alone or in a composite, and thereby an environmental catalyst having a more excellent catalytic action such as a decomposition function. Can be configured. In addition, the environmental catalyst provided with the above-mentioned carbon catalyst can also be used as a purification catalyst for water treatment as well as the above-described exhaust gas purification catalyst.

Further, the nitrogen-containing carbon alloy of the present invention can be widely used as a catalyst for chemical reaction, and in particular, can be used as a substitute for a platinum catalyst. That is, the above-mentioned carbon catalyst can be used as a substitute for a general process catalyst for the chemical industry containing a noble metal such as platinum. For this reason, according to the above-mentioned carbon catalyst, a low-cost chemical reaction process catalyst can be provided without using expensive noble metals such as platinum. Furthermore, since the above-mentioned carbon catalyst has a large specific surface area, it can constitute a chemical reaction process catalyst excellent in chemical reaction efficiency per unit volume.
Such a carbon catalyst for chemical reaction is applied to, for example, a hydrogenation reaction catalyst, a dehydrogenation reaction catalyst, an oxidation reaction catalyst, a polymerization reaction catalyst, a reforming reaction catalyst, and a steam reforming catalyst. be able to. More specifically, it is possible to apply a carbon catalyst to each chemical reaction with reference to a catalyst related literature such as “Catalyst Preparation (Kodansha) by Takaho Shirasaki and Naoyuki Todo, 1975”.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the examples shown below. Unless otherwise specified, “part” is based on mass.

<Method for evaluating properties of nitrogen-containing carbon alloy>
(Specific surface area measurement by BET method)
About the nitrogen-containing carbon alloy sample before acid cleaning, and the nitrogen-containing carbon alloy sample isolated after acid cleaning, using a sample pretreatment device (BELPREPE-flow (trade name) manufactured by Nippon Bell Co., Ltd.), nitrogen-containing carbon alloy The sample was dried under vacuum at 200 ° C. for 3 hours.
The specific surface area of the nitrogen-containing carbon alloy was measured under simple measurement conditions using an automatic specific surface area / pore distribution measuring device (BELSORP-miniII (trade name) manufactured by Bell Japan).
The specific surface area was determined by the BET (Brunauer-Emmett-Teller) method using an analysis program installed in the apparatus.

Example 1
<Carbon Material Synthesis of Iron (II) Chloride Tetrahydrate Addition (4-Py) ₃ -TAz Mixture (1C)>
(Preparation of (4-Py) ₃ -TAz)
New J.M. Chem. , 2006, 30, 1276-1281. (4-Py) ₃ -TAz was adjusted with reference to FIG. 4-cyanopyridine 10 g, 18-crown-6 10 g, KOH 225 mg, and decalin 10 mL were mixed and stirred at 200 ° C. for 5 hours. After air cooling to room temperature, the reaction product was filtered and washed by boiling with pyridine. The obtained solid was dissolved in 1N hydrochloric acid, and the solid was precipitated with aqueous ammonia, filtered, washed with water and dried to obtain 7.1 g of (4-Py) ₃ -TAz.

Molecular formula: C ₁₈ H ₁₂ N ₆ , molecular weight: 312.33
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Preparation of iron (II) chloride tetrahydrate (4-Py) ₃ -TAz mixture)
After adding 6.30 g of the above (4-Py) ₃ -TAz and 6.30 g of iron (II) chloride tetrahydrate, mechanically pulverized and mixed to add iron (II) chloride tetrahydrate (4-Py ) ₃ -TAz mixture (1A) was obtained.

(Infusibilization and carbonization treatment)
Iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (1A) 3.110 g was measured into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) quartz It was installed in the center of the tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (1B) 0.7923g.

(Crushing, acid cleaning treatment, specific surface area measurement)
Carbon material (1B) was pulverized in an agate mortar to obtain an acid-free carbon material. The result of measuring the specific surface area of the obtained acid-free carbon material by the BET method is shown in the column before acid cleaning in Table 1 below.
The acid-free washed carbon material obtained by pulverizing the carbon material (1B) in an agate mortar was repeatedly washed with concentrated hydrochloric acid, centrifuged, and the supernatant was removed until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.5334 g of acid-washed carbon material (1C). The obtained acid-washed carbon material (1C) was used as the nitrogen-containing carbon alloy of Example 1. The result of measuring the specific surface area by the BET method is shown in the column after acid cleaning in Table 1 below.

1. Oxygen reduction reaction (ORR) activity of carbon alloy coated electrode (preparation of carbon alloy coated electrode)
To 10 mg of the obtained nitrogen-containing carbon alloy material of Example 1, 110 mg of Nafion solution (5% alcohol aqueous solution) as a binder, 2.4 mL of water as a solvent and 1.6 mL of 1-propanol (IPA) are added, and a 7 mmφ attachment is added. Was dispersed for 30 minutes with an ultrasonic homogenizer (Nissei Co., Ltd., US-150T (trade name)). Using a rotating ring disk electrode (HR2-RD1-Pt8 / GC5 (trade name) manufactured by Hokuto Denko), the nitrogen-containing carbon alloy dispersion is placed on the carbon electrode so that the nitrogen-containing carbon alloy is 0.05 mg / cm ^2. It was applied and dried at room temperature to obtain a carbon alloy coated electrode.

(Measurement of oxygen reduction reaction (ORR) activity of carbon alloy coated electrode)
A rotating electrode device (Hokuto Denko Co., Ltd., HR-201 (Brand name)) is connected to an Automatic Polarization System (Hokuto Denko Co., Ltd., HZ-3000 (Brand name)). The obtained carbon alloy-coated electrode, counter electrode and reference electrode were measured by the following procedure using a platinum electrode and a saturated calomel electrode (SCE), respectively.
A. For cleaning the carbon alloy material-coated electrode, a sweep potential of 0.946 to −0.204 V (vs. SCE), a sweep rate of 50 mV / s in a 0.1 M sulfuric acid aqueous solution bubbled with argon at 30 ° C. for 30 minutes or more, Ten cycles of cyclic voltammetry were measured.
B. Linear measurement at a sweep potential of 0.746 to -0.204 V (vs. SCE), a sweep speed of 5 mV / s, and an electrode rotation speed of 1500 rpm in a 0.1 M sulfuric acid aqueous solution in which argon was bubbled for 30 minutes or more for blank measurement. Sweep voltammetry was measured.
C. In order to measure the oxygen reduction activity, a linear sweep was performed at a sweep potential of 0.746 to -0.204 V (vs. SCE), a sweep speed of 5 mV / s, and an electrode rotation speed of 1500 rpm in a 0.5 M sulfuric acid aqueous solution bubbled with oxygen for 30 minutes or more. Voltammetry was measured.
D. The measurement data of B was subtracted from the measurement data of C and adopted as the true oxygen reduction activity. From the obtained voltammogram (voltage-current density curve), a voltage (V vs. RHE) at a current density of −1 mA / cm ² was determined and used as an ORR activity value.
The obtained results are shown in Table 1 below.

(Example 2)
<Carbon Material Synthesis of Cobalt (II) Chloride Hexahydrate Addition (4-Py) ₃ -TAz Mixture (2C)>
After adding 1.60 g of (4-Py) ₃ -TAz and 1.60 g of cobalt (II) hexahydrate, mechanically pulverized and mixed to add cobalt (II) hexahydrate (4-Py) _{A 3-} TAz mixture (2A) was obtained.

(Infusibilization and carbonization treatment)
Cobalt (II) chloride hexahydrate added (4-Py) ₃ -TAz mixture (2A) 3.1559 g was weighed into a quartz boat and inserted into a tube furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz It was installed in the center of the tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (2B) 1.0901g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (2B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.6635 g of acid-washed carbon material (2C). The obtained acid cleaned carbon material (2C) was used as the nitrogen-containing carbon alloy of Example 2. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 2 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 3
<Carbon Material Synthesis of Iron (II) Chloride Tetrahydrate Addition (3-Py) ₃ -TAz Mixture (3C)>
(Preparation of (3-Py) ₃ -TAz)
(4-Py) _3- TAz was prepared under the same conditions as in the preparation method. 10 g of 3-cyanopyridine, 10 g of 18-crown-6, 225 mg of KOH, and 10 mL of decalin were mixed and stirred at 200 ° C. for 5 hours. After air cooling to room temperature, the reaction product was filtered and washed by boiling with pyridine. The obtained solid was dissolved in 1N hydrochloric acid, the solid was precipitated with aqueous ammonia, filtered, washed with water and dried to obtain (3-Py) ₃ -TAz in a yield of 4.1 g.

Molecular formula: C ₁₈ H ₁₂ N ₆ , molecular weight: 312.33
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Preparation of iron (II) chloride tetrahydrate (3-Py) ₃ -TAz mixture)
After adding 1.60 g of the above (3-Py) ₃ -TAz and 1.60 g of iron (II) chloride tetrahydrate, mechanically pulverized and mixed to add iron (II) chloride tetrahydrate (3-Py ) ₃ -TAz mixture (3A) was obtained.

(Infusibilization and carbonization treatment)
Iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (3A) 3.1360 g was measured into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) quartz It was installed in the center of the tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (3B) 0.7259g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.4564 g of acid-cleaned carbon material (3C). The obtained acid cleaned carbon material (3C) was used as the nitrogen-containing carbon alloy of Example 3. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 3 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 4
<Carbon Material Synthesis of Cobalt (II) Chloride Hexahydrate Addition (3-Py) _3- TAz Mixture (4C)>
(Preparation of cobalt (II) chloride hexahydrate (3-Py) ₃ -TAz mixture)
After adding 6.30 g of the above (3-Py) ₃ -TAz and 6.30 g of cobalt (II) chloride hexahydrate, mechanically pulverized and mixed to add cobalt chloride (II) hexahydrate (3-Py ) ₃ -TAz mixture (4A) was obtained.

(Infusibilization and carbonization treatment)
Cobalt (II) chloride hexahydrate added (3-Py) ₃ -TAz mixture (4A) 3.1118 g was measured in a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) quartz It was installed in the center of the tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (4B) 1.0555g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (4B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.6443 g of acid-cleaned carbon material (4C). The obtained acid-washed carbon material (4C) was used as the nitrogen-containing carbon alloy of Example 4. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 4 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 5)
<Carbon Material Synthesis of FeAA2, Iron Chloride (II) Tetrahydrate Addition (4-Py) ₃ -TAz Mixture (5C)>
(FeAA2, Fe (II) chloride tetrahydrate added (4-Py) ₃ -TAz mixture preparation)
After adding the above (4-Py) ₃ -TAz 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed, FeAA2 and iron (II) chloride 4 water A Japanese addition (4-Py) ₃ -TAz mixture (5A) was obtained.

Molecular formula: C ₁₀ H ₁₄ Fe ₁ O ₄ , molecular weight: 254.061
Elemental analysis (calculated values): C, 47.27; H, 5.55; Fe, 21.98; O, 25.19

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (5A) 3.1959 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (5B) 1.2519g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and allowed to stand overnight to obtain 0.6562 g of an acid cleaned carbon material (5C). The obtained acid cleaned carbon material (5C) was used as the nitrogen-containing carbon alloy of Example 5. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 5 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 6)
<FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -TAz mixture carbon material synthesis (6C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (5A) (3.1769 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C. to 800 ° C. by 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (6B) 0.8955g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (6B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.5988 g of acid-washed carbon material (6C). The obtained acid cleaned carbon material (6C) was used as the nitrogen-containing carbon alloy of Example 6. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 6 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 7)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py) ₃ -TAz mixture carbon material synthesis (7C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (5A) 3.1134 g was weighed into a quartz boat, and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C to 900 ° C at 5 ° C per minute and held at 900 ° C for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (7B) 0.8122g.

(Crushing, water washing treatment, specific surface area measurement)
The carbon material (7B) was pulverized with an agate mortar, washed with water, filtered and air-dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight as it was to obtain a non-acid cleaned carbon material (7C). The obtained non-acid cleaned carbon material (7C) was used as the nitrogen-containing carbon alloy of Example 7. The specific surface area was measured by the BET method. The results are shown in the column before acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 7 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 8)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py) ₃ -TAz mixture carbon material synthesis (8C)>

(Crushing, acid cleaning treatment, specific surface area measurement)
The non-acid-cleaned carbon material (7C) was pulverized in an agate mortar, and concentrated hydrochloric acid cleaning, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.5040 g of acid-cleaned carbon material (8C). The obtained acid-washed carbon material (8C) was used as the nitrogen-containing carbon alloy of Example 8. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 8 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 9
<Carbon Material Synthesis of FeAA2, Iron (II) Chloride Tetrahydrate Addition (4-Py) ₃ -TAz Mixture (9C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (5A) (3.2067 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter: 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C. per minute and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (9B) 0.8220g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (9B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.5407 g of acid-washed carbon material (9C). The obtained acid-washed carbon material (9C) was used as the nitrogen-containing carbon alloy of Example 9. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 9 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 10)
<Carbon Material Synthesis of FeAA2, Iron (II) Chloride Tetrahydrate Addition (3-Py) ₃ -TAz Mixture (10C)>
(FeAA2, Fe (II) chloride tetrahydrate added (3-Py) ₃ -TAz mixture preparation)
(3-Py) ₃ -TAz 6.30 g, FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g was added, then mechanically pulverized and mixed, FeAA2 and iron (II) chloride tetrahydrate added A (3-Py) _3- TAz mixture (10A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron (II) chloride tetrahydrate added (3-Py) ₃ -TAz mixture (10A) 3.1936 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (10B) 1.1322g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (10B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Furthermore, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.6234 g of acid-cleaned carbon material (10C). The obtained acid-washed carbon material (10C) was used as the nitrogen-containing carbon alloy of Example 10. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 10 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 11)
<FeAA2, iron (II) chloride tetrahydrate added (3-Py) ₃ -TAz mixture carbon material synthesis (11C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2 and iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture (10A) (3.0646 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C. to 800 ° C. by 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (11B) 0.8184g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (11B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.5646 g of acid-washed carbon material (11C). The obtained acid-washed carbon material (11C) was used as the nitrogen-containing carbon alloy of Example 11. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 11 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 12)
<Carbon Material Synthesis of FeAA2, Iron Chloride (II) Tetrahydrate Addition (3-Py) ₃ -TAz Mixture (12C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture (10A) (3.0131 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter: 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C to 900 ° C at 5 ° C per minute and held at 900 ° C for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (12B) 0.7353g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (12B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.5141 g of acid-washed carbon material (12C). The obtained acid cleaned carbon material (12C) was used as the nitrogen-containing carbon alloy of Example 12. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 12 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 13)
<Carbon Material Synthesis of FeAA2, Iron (II) Chloride Tetrahydrate Addition (3-Py) ₃ -TAz Mixture (13C)>
(Infusibilization and carbonization treatment)
The above-described FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture (10A) (3.0748 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature. The temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C. per minute and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (13B) 0.8436g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (13B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.5610 g of acid-cleaned carbon material (13C). The obtained acid cleaned carbon material (13C) was used as the nitrogen-containing carbon alloy of Example 13. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 13 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 14)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py) ₃ -Py mixture carbon material synthesis (14C)>
(Preparation of (4-Py) ₃ -Py)
CrystEngCom, 2011, 13, 6864-6870. (4-Py) ₃ -Py was adjusted. 1.21 g of 4-acetylpyridine and 0.54 g of pyridine-4-carboxaldehyde were dissolved in 40 mL of ethanol, 0.62 g of KOH and 20 mL of 32% aqueous ammonia were added, and the mixture was stirred at room temperature for 24 hours. The precipitated solid was filtered, washed with water and ethanol, dried and recrystallized with ethanol to obtain 1.00 g of (4-Py) ₃ -Py.

Molecular formula: C ₂₀ H ₁₄ N ₄ , molecular weight: 310.35
Elemental analysis (calculated value): C, 77.40, H, 4.55, N, 18.05

(FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -Py mixture preparation)
After adding the above (4-Py) ₃ -Py 6.30 g, FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed, FeAA2, iron chloride (II) tetrahydrate Product addition (4-Py) ₃ -Py mixture (14A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (14A) 3.2001 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (14B) 1.5185g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (14B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.8111 g of acid-washed carbon material (14C). The obtained acid-washed carbon material (14C) was used as the nitrogen-containing carbon alloy of Example 14. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 14 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 15)
<FeAA2, iron chloride (II) tetrahydrate added (4-MePy) ₃ -TAz / I mixture carbon material synthesis (15C)>
(Preparation of FeAA2, (4-MePy) ₃ -TAz / I)
Liebigs Analder der Chemie, 1991, 10, 1021-1028. (4-MePy) ₃ -TAz / I was adjusted with reference to FIG. (4-Py) ₃ -TAz 0.30 g, MeI 0.54 g, and DMF ₅ mL described in Example 1 were placed in an autoclave and stirred at 90 ° C. for 4 days. After air cooling, the precipitate was filtered, washed with acetone and dried to obtain 0.55 g of (4-MePy) ₃ -TAz / I.

Molecular formula: C ₂₁ H ₂₁ I ₃ N ₆ , molecular weight: 738.15
Elemental analysis (calculated values): C, 34.17, H, 2.87, I, 51.58, N, 11.39

(FeAA2, iron (II) chloride tetrahydrate added (4-MePy) ₃ -TAz / I mixture preparation)
After adding the above (4-MePy) ₃ -TAz / I 6.30 g, FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed, FeAA2, iron chloride (II) Tetrahydrate addition (4-MePy) _3- TAz / I mixture (15A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-MePy) ₃ -TAz / I mixture (15A) 2.0237 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3. 6 cmφ) was installed in the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (15B) 0.5176g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (15B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3096 g of acid-washed carbon material (15C). The obtained acid cleaned carbon material (15C) was used as the nitrogen-containing carbon alloy of Example 15. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 15 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 16)
<Refiring and acid treatment of carbon material of FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture (16C)>
(Infusibilization and carbonization treatment firing method A)
0.5179 g of the acid-cleaned carbon material (5C) of Example 5 was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. The mixture was circulated for 200 minutes for 30 minutes at room temperature. In addition, the baking method A is a baking method which implements only substitution by nitrogen circulation.
Nitrogen was lowered to 20 mL / min during the temperature increase, and the temperature was increased from 30 ° C. to 1000 ° C. at 5 ° C./min and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (16B) 0.4254g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (16B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.3645 g of acid-washed carbon material (16C). The obtained acid cleaned carbon material (16C) was used as the nitrogen-containing carbon alloy of Example 16. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
To 25 mg of the nitrogen-containing carbon alloy material obtained in Example 16, 220 mg of Nafion solution (5% alcohol aqueous solution) as a binder, 2.4 mL of water as a solvent, and 1.6 mL of 1-propanol (IPA) were added. In the same manner as above, a nitrogen-containing carbon alloy dispersion was prepared, and the nitrogen-containing carbon alloy dispersion was applied onto the carbon electrode so that the nitrogen-containing carbon alloy was 0.5 mg / cm ² , and dried at room temperature. The ORR activity value was measured in the same manner as in Example 1 except that a carbon alloy-coated electrode was produced. The results are shown in Table 1 below.

(Example 17)
<FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -TAz mixture carbon material refiring and acid treatment (17C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
0.5095 g of the acid-washed carbon material (5C) of Example 5 was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement furnace, and nitrogen was added. Was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. In addition, the firing method B is a firing method in which the operation of deaeration with a vacuum pump and then nitrogen replacement is repeated three times.
Thereafter, nitrogen was lowered to 20 mL / min during the temperature rise, and the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (17B) 0.3915g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (17B) was pulverized with an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.3677 g of acid-washed carbon material (17C). The obtained acid-washed carbon material (17C) was used as the nitrogen-containing carbon alloy of Example 17. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 17 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 18)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture carbon material refiring and acid treatment (18C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weighing 0.21658 g of the acid-cleaned carbon material of Example 5 (5C) into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. The firing method C is a firing method in which after degassing with a vacuum pump, the operation of replacing nitrogen is repeated three times, and the sample tube is rotated at 1.3 rpm during firing in a rotary furnace.
Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (18B) 0.1704g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (18B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1462 g of acid-washed carbon material (18C). The obtained acid-washed carbon material (18C) was used as the nitrogen-containing carbon alloy of Example 18. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 18 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 19)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture carbon material refiring and acid treatment (19C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weigh out 0.2327 g of the acid-cleaned carbon material (6C) of Example 6 in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (19B) 0.2121g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (19B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.1677 g of acid-washed carbon material (19C). The obtained acid cleaned carbon material (19C) was used as the nitrogen-containing carbon alloy of Example 19. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 19 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 20)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture carbon material refiring and acid treatment (20C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.3761 g of the acid-cleaned carbon material (8C) of Example 8 was measured on a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (20B) 0.3210g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (20B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.2887 g of the acid-washed carbon material (20C). The obtained acid-washed carbon material (20C) was used as the nitrogen-containing carbon alloy of Example 20. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 20 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 21)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture carbon material refiring and acid treatment (21C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
The acid-cleaned carbon material (9C) of Example 9 (0.3588 g) was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (21B) 0.3486g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (21B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.3264 g of acid-washed carbon material (21C). The obtained acid cleaned carbon material (21C) was used as the nitrogen-containing carbon alloy of Example 21. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 21 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 22)
<FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture carbon material refiring and acid treatment (22C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.4830 g of the acid-cleaned carbon material (10C) of Example 10 was measured in a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (22B) 0.4743g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (22B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3832 g of acid-cleaned carbon material (22C). The obtained acid cleaned carbon material (22C) was used as the nitrogen-containing carbon alloy of Example 22. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 22 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 23)
<Refiring and acid treatment of carbon material of FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture (23C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.4239 g of the acid-cleaned carbon material (11C) of Example 11 was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (23B) 0.3752g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (23B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.3481 g of acid-washed carbon material (23C). The obtained acid-washed carbon material (23C) was used as the nitrogen-containing carbon alloy of Example 23. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 23 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 24)
<Refiring and acid treatment of carbon material of FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture (24C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.3881 g of the acid-cleaned carbon material (12C) of Example 12 was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (24B) 0.3848g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (24B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3104 g of acid-cleaned carbon material (24C). The obtained acid-washed carbon material (24C) was used as the nitrogen-containing carbon alloy of Example 24. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 24 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 25)
<FeAA2, iron chloride (II) tetrahydrate added (3-Py) ₃ -TAz mixture carbon material refiring and acid treatment (25C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.4201 g of the acid-cleaned carbon material of Example 13 (13C) was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (25B) 0.3466g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (25B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.3019 g of an acid cleaned carbon material (25C). The obtained acid cleaned carbon material (25C) was used as the nitrogen-containing carbon alloy of Example 25. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 25 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 26)
<FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -Py mixture carbon material refiring and acid treatment (26C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weighing 0.2360 g of the acid-cleaned carbon material of Example 14 (14C) into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (26B) 0.1924g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (26B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1370 g of acid-washed carbon material (26C). The obtained acid-washed carbon material (26C) was used as the nitrogen-containing carbon alloy of Example 26. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 26 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 27)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py) _3- TAz mixture carbon material activation and acid treatment (27C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
0.460 g of acid-cleaned carbon material (8C) of Example 8 was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, the nitrogen was reduced to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and when the temperature reached 1000 ° C., the quartz tube was rotated at 1.3 rpm. After holding at 1000 ° C. for 40 minutes, the nitrogen was switched to nitrogen mixed with 10% CO ₂ (20 mL per minute) and held for 20 minutes. Then, it cooled to room temperature over 3 hours, and obtained 0.3053g of carbon materials (27B).

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (27B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.2793 g of acid-cleaned carbon material (27C). The obtained acid cleaned carbon material (27C) was used as the nitrogen-containing carbon alloy of Example 27. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 27 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 28)
<Ammonia activation and acid treatment (28C) of carbon material of FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -TAz mixture>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weigh out 0.2093 g of the acid-cleaned carbon material (8C) of Example 8 in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, the nitrogen was reduced to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and when the temperature reached 1000 ° C., the quartz tube was rotated at 1.3 rpm. After holding at 1000 ° C. for 40 minutes, the nitrogen was changed to nitrogen mixed with 10% NH ₃ (20 mL / min) and held for 20 minutes. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (28B) 0.1176g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (28B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.1053 g of acid-washed carbon material (28C). The obtained acid-washed carbon material (28C) was used as the nitrogen-containing carbon alloy of Example 28. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 28 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 30)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) _2- TAz mixture carbon material synthesis (30C)>
(Preparation of (4-Py) ₂ -TAz)

Tetrahedron, 1976, 32, 615. (4-Py) ₂ -TAz was synthesized with reference to FIG. 2.60 g of 4-cyanopyridine and 59 mg of NaOMe were dissolved in 7.5 mL of MeOH. After stirring at room temperature for 4 hours, 2.03 g of formamidine hydrochloride in DMF was added dropwise and stirred for 16 hours. After distilling off the solvent, the mixture was stirred at 125 ° C. for 16 hours, 25 mL of water was added, and the precipitated solid was washed with water and toluene to obtain 2.5 g of (4-Py) ₂ -TAz.

Molecular formula: C ₁₃ H ₉ N _5, molecular weight: 235.24
Elemental analysis (calculated values): C, 66.37, H, 3.86, N, 29.77

(FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₂ -TAz mixture preparation)
After adding the above-mentioned (4-Py) ₂ -TAz 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed to obtain FeAA2 and iron (II) chloride tetrahydrate. Product addition (4-Py) _2- TAz mixture (30A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₂ -TAz mixture (30A) (3.31916 g) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter 3. 6 cmφ) was placed in the center of the quartz tube, and nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 800 ° C. by 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (30B) 0.6708g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (30B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.4573 g of acid-cleaned carbon material (30C). The obtained acid-washed carbon material (30C) was used as the nitrogen-containing carbon alloy of Example 30. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 30 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 40)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₂ -TAz mixture carbon material refiring and acid treatment (40C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weighing 0.2536 g of the acid-cleaned carbon material (30C) of Example 30 into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas-substitution rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 1.3 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (40B) 0.2617g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (40B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.1837 g of acid-cleaned carbon material (40C). The obtained acid-washed carbon material (40C) was used as the nitrogen-containing carbon alloy of Example 40. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 40 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 31)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py) ₂ Ph-TAz mixture carbon material synthesis (31C)>
(Preparation of (4-Py) ₂ Ph-TAz)

Chem. Commun. , 2002, 1356. , 27.3 mL of HNMe ₂ (2M THF solution) was dissolved in 500 mL of diethyl ether under a nitrogen stream, and 21 mL of n-BuLi (2.6M hexane solution) was added dropwise at −78 ° C. After raising the temperature to 0 ° C., benzonitrile was added dropwise, the temperature was returned to room temperature, and stirring was continued for 15 hours. Water was added, the precipitated solid was filtered, washed with water and MeOH, and dried to obtain 8.5 g of (4-Py) ₂ Ph-TAz.

Molecular formula: C ₁₉ H ₁₃ N ₅ , molecular weight: 311.34
Elemental analysis (calculated values): C, 73.30, H, 4.21, N, 22.49

(FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₂ Ph-TAz mixture preparation)
After adding the above (4-Py) ₂ Ph-TAz 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed, FeAA2 and iron (II) chloride 4 water A Japanese addition (4-Py) ₂ Ph-TAz mixture (31A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₂ Ph-TAz mixture (31A) 3.2291 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ). ) And was circulated at room temperature for 200 minutes per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C. per minute and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (31B) 0.6304g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (31B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.4526 g of acid-washed carbon material (31C). The obtained acid-washed carbon material (31C) was used as the nitrogen-containing carbon alloy of Example 31. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 31 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 41)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₂ Ph-TAz mixture carbon material refiring and acid treatment (41C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
0.1872 g of the acid-cleaned carbon material (31C) of Example 31 was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (41B) 0.1685g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (41B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1496 g of acid-cleaned carbon material (41C). The obtained acid cleaned carbon material (41C) was used as the nitrogen-containing carbon alloy of Example 41. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 41 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 32)
<FeAA2, Fe (II) chloride tetrahydrate added (4-Py-≡-) ₃ -TAz mixture carbon material synthesis (32C)>
(Preparation of 4-Py-≡-OH)

JOC, 2001, 66, 7402. As a reference, 4-Py-≡-OH was synthesized. Dissolve in 5.01 g of 4-bromopyridine hydrochloride, 180 mg of Pd (PPh ₃ ) ₂ Cl ₂ , 29 mg of CuI, 43 mL of THF, add 17 mL of NHEt ₂ and stir at 45 ° C. under nitrogen flow for 4.5 hours. did. The solvent was distilled off under reduced pressure, extracted and washed with chloroform and water, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (chloroform: ethyl acetate = 1: 1) and recrystallization from chloroform and hexane gave 3.80 g of 4-Py-≡-OH.

(Preparation of 4-Py-≡)

  JOC, 2001, 66, 7402. As a reference, 4-Py-≡ was synthesized. 3.00 g of 4-Py-≡-OH and 0.80 g of NaOH (ground) were dissolved in 90 mL of toluene and heated to reflux for 3 hours. After removing the residue, the solvent was distilled off under reduced pressure, and 1.22 g of 4-Py-≡ was obtained by sublimation purification.

(Preparation of (4-Py-≡-) ₃ -TAz)

2.41 g of 4-Py-≡ was dissolved in 200 mL of THF, 9.9 mL of n-BuLi (2.6 M hexane solution) was added dropwise at −78 ° C. under a nitrogen stream, and the mixture was stirred for 30 minutes. 08 g of cyanuric chloride in 60 mL of THF was added dropwise, and after stirring for 7 hours, water and ethyl acetate were added, the mixture was returned to room temperature, the precipitated solid was filtered, washed with water, ethyl acetate and MeOH, dried and 2.4 g of ( 4-Py-≡-) _3- TAz (black solid) was obtained.

Molecular formula: C ₂₄ H ₁₂ N ₆ , molecular weight: 384.39
Elemental analysis (calculated values): C, 74.99, H, 3.15, N, 21.86

(FeAA2, iron (II) chloride tetrahydrate added (4-Py-≡-) ₃ -TAz mixture preparation)
After adding the above (4-Py-≡-) ₃ -TAz 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed to obtain FeAA2 and iron (II) chloride. A tetrahydrate added (4-Py-≡-) ₃ -TAz mixture (32A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (4-Py-≡-) ₃ -TAz mixture (32A) 3.1443 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3 .6 cmφ) at the center of the quartz tube and nitrogen was circulated at 200 mL / min for 30 minutes at room temperature.
The temperature was raised from 30 ° C to 900 ° C at 5 ° C per minute and held at 900 ° C for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (32B) 1.1595g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (32B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Furthermore, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.7823 g of acid-washed carbon material (32C). The obtained acid cleaned carbon material (32C) was used as the nitrogen-containing carbon alloy of Example 32. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 32 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 42)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py-≡-) ₃ -TAz mixture carbon material refiring and acid treatment (42C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
The acid-cleaned carbon material (32C) 0.3465 g of Example 32 was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (42B) 0.3331g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (42B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.3109 g of acid-washed carbon material (42C). The obtained acid cleaned carbon material (42C) was used as the nitrogen-containing carbon alloy of Example 42. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 42 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 33)
<Synthesis of carbon material of FeAA2, iron chloride (II) tetrahydrate added 4,4'-Py-Py mixture (33C)>

(Preparation of FeAA2, iron chloride (II) tetrahydrate added 4,4'-Py-Py mixture)
After adding the above 4,4′-Py-Py 6.30 g (manufactured by Wako Pure Chemical Industries, Ltd.), 0.403 g of FeAA2, and 6.30 g of iron (II) chloride tetrahydrate, mechanically pulverized and mixed, FeAA2, An iron (II) chloride tetrahydrate-added 4,4′-Py-Py mixture (33A) was obtained.

Molecular formula: C ₁₀ H ₈ N ₂ , molecular weight: 156.18
Elemental analysis (calculated value): C, 76.90, H, 5.16, N, 17.94

(Infusibilization and carbonization treatment)
We measured 3.1826 g of FeAA2, iron chloride (II) tetrahydrate added 4,4'-Py-Py mixture (33A) in a quartz boat and inserted it into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (33B) 0.7579g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (33B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.4257 g of acid-washed carbon material (33C). The obtained acid cleaned carbon material (33C) was used as the nitrogen-containing carbon alloy of Example 33. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 33 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 43)
<Refiring and Acid Treatment of Carbon Material of FeAA2, Iron (II) Chloride Tetrahydrate Added 4,4'-Py-Py Mixture (43C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
Weighing 0.3116 g of the acid-cleaned carbon material (33C) of Example 33 into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (43B) 0.2692g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (43B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.2123 g of acid-cleaned carbon material (43C). The obtained acid cleaned carbon material (43C) was used as the nitrogen-containing carbon alloy of Example 43. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 43 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 34)
<Synthesis of Carbon Material of FeAA2, Iron Chloride Tetrahydrate Added 3,3′-Py-Py Mixture (34C)>

(Preparation of FeAA2, iron (II) chloride tetrahydrate added 3,3′-Py-Py mixture)
3,3′-Py-Py 6.30 g (manufactured by Tokyo Chemical Industry Co., Ltd.), FeAA2 0.403 g, iron chloride (II) tetrahydrate 6.30 g were added, and then mechanically pulverized and mixed to obtain FeAA2, iron chloride (II ) A tetrahydrate-added 3,3′-Py-Py mixture (34A) was obtained.

Molecular formula: C ₁₀ H ₈ N ₂ , molecular weight: 156.18
Elemental analysis (calculated value): C, 76.90, H, 5.16, N, 17.94

(Infusibilization and carbonization treatment)
1.2000 g of FeAA2, iron chloride (II) tetrahydrate added 3,3′-Py-Py mixture (34A) was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (34B) 0.2014g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (34B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.1562 g of acid-washed carbon material (34C). The obtained acid-washed carbon material (34C) was used as the nitrogen-containing carbon alloy of Example 34. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 34 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 44)
<Refiring and acid treatment of carbon material of FeAA2, iron chloride (II) tetrahydrate added 3,3'-Py-Py mixture (44C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
0.0886 g of the acid-cleaned carbon material (34C) of Example 34 was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (44B) 0.0689g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (44B) was pulverized with an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.0554 g of an acid cleaned carbon material (44C). The obtained acid cleaned carbon material (44C) was used as the nitrogen-containing carbon alloy of Example 44. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 44 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 35)
<Carbon material synthesis of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethylene mixture (35C)>

(Preparation of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethylene mixture)
1,2- (4-Py) 2-Ethylene 6.30 g (manufactured by ALDRICH), FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g were added, and then mechanically pulverized and mixed to obtain FeAA2, chloride. An iron (II) tetrahydrate-added 1,2- (4-Py) 2-Ethylene mixture (35A) was obtained.

Molecular formula: C ₁₂ H ₁₀ N ₂ , molecular weight: 182.22
Elemental analysis (calculated values): C, 79.10, H, 5.53, N, 15.37

(Infusibilization and carbonization treatment)
Feal 2 and iron chloride (II) tetrahydrate added 1,2- (4-Py) 2-Ethylene (35A) 3.1772 g was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter) It was installed at the center of a quartz tube of 3.6 cmφ, and nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (35B) 0.8691g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (35B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.4752 g of acid-washed carbon material (35C). The obtained acid-washed carbon material (35C) was used as the nitrogen-containing carbon alloy of Example 35. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 35 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 45)
<Refiring and acid treatment (45C) of carbon material of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethylene mixture>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement furnace)
Weighing 0.2146 g of the acid-cleaned carbon material of Example 35 (35C) into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (45B) 0.1867g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (45B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1604 g of an acid cleaned carbon material (45C). The obtained acid-washed carbon material (45C) was used as the nitrogen-containing carbon alloy of Example 45. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 45 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 36)
<Carbon material synthesis of FeAA2, iron chloride (II) tetrahydrate added (4-Py) (2-Py) ₂ -TAz mixture (36C)>
(Adjustment of (4-Py) (2-Py) ₂ -TAz)
Chem. Comm, 2002, 1356-1357. (4-Py) (2-Py) _2- TAz was adjusted with reference to FIG.
200 mg of NaH was added to 5 g of 4-cyanopyridine and 5 g of 2-cyanopyridine, heated at 180 ° C. for 30 minutes, cooled to room temperature, dissolved in 500 mL of toluene by heating, and filtered. The obtained toluene solution was extracted with an aqueous solution obtained by dissolving 3 g of NiCl ₂ .6H ₂ O in 200 mL of deionized water, 5 g of KCN was added thereto, the resulting precipitate was filtered and dried, recrystallized with ethanol, (4-Py) and _(2-Py) 2 TAz give 2g.

Molecular formula: C ₂₀ H ₁₄ N ₄ , molecular weight: 310.35
Elemental analysis (calculated value): C, 77.40, H, 4.55, N, 18.05

(FeAA2, iron (II) chloride tetrahydrate added (4-Py) (2-Py) ₂ -TAz mixture preparation)
After adding the above-mentioned (4-Py) (2-Py) ₂ -TAz 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverizing and mixing, FeAA2 and iron chloride ( II) Tetrahydrate added (4-Py) (2-Py) ₂ -TAz mixture (36A) was obtained.

(Infusibilization and carbonization treatment)
3.1877 g of FeAA2, iron chloride (II) tetrahydrate added (4-Py) (2-Py) ₂ -TAz mixture (36A) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ ( It was installed in the center of a quartz tube having an inner diameter of 3.6 cmφ, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (36B) 1.2970g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (36B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.6788 g of acid-washed carbon material (36C). The obtained acid cleaned carbon material (36C) was used as the nitrogen-containing carbon alloy of Example 36. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 36 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 46)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) (2-Py) _2- TAz mixture carbon material refiring and acid treatment (46C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement furnace)
Weighing 0.5099 g of the acid-cleaned carbon material (36C) of Example 36 into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (46B) 0.4191g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (46B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3840 g of acid-washed carbon material (46C). The obtained acid cleaned carbon material (46C) was used as the nitrogen-containing carbon alloy of Example 46. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 46 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 50)
<Carbon material synthesis of FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ Ph-TAz mixture (50C)>
(Preparation of (4-Py) ₃ -Ph)

Organic Lett. , 2008, 10, 2513. (4-Py) ₃ -Ph was synthesized with reference to FIG. 157 mg 1,3,5-tribromobenzene, 250 mg 4-pyridineboronic acid, 80 mg Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , 1.60 g of sodium carbonate was dissolved in 20 mL of 1,4-dioxane and 20 mL of pure water, degassed by nitrogen bubbling, and then heated to reflux for 30 hours. After extraction with dichloromethane and evaporation of the solvent, the residue was purified by alumina column chromatography (chloroform). Finally, 4.9 g of (4-Py) ₃ -Ph was obtained by MeOH cooking.

Molecular formula: C ₂₁ H ₁₅ N ₃ , molecular weight: 309.36
Elemental analysis (calculated values): C, 81.53, H, 4.89, N, 13.58

(FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -Ph mixture preparation)
After adding the above-mentioned (4-Py) ₃ -Ph 6.30 g, FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed to obtain FeAA2 and iron (II) chloride tetrahydrate. Product addition (4-Py) _3- Ph mixture (50A) was obtained.

(Infusibilization and carbonization treatment)
FeAA2, iron (II) chloride tetrahydrate added (4-Py) ₃ -Ph mixture (50A) 2.0432 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C to 900 ° C at 5 ° C per minute and held at 900 ° C for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (50B) 0.8524g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (50B) was pulverized with an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and then left overnight to obtain 0.5957 g of acid-washed carbon material (50C). The obtained acid cleaned carbon material (50C) was used as the nitrogen-containing carbon alloy of Example 50. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 50 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 60)
<FeAA2, iron chloride (II) tetrahydrate added (4-Py) ₃ -Ph mixture carbon material refiring and acid treatment (60C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement)
Weighing 0.3017 g of the acid-cleaned carbon material (50C) of Example 50 into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (60B) 0.2975g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (60B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.2314 g of acid-cleaned carbon material (60C). The obtained acid cleaned carbon material (60C) was used as the nitrogen-containing carbon alloy of Example 60. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 60 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 51)
<Carbon Material Synthesis of FeAA2, Iron Chloride (II) Tetrahydrate Addition (HIm) ₃ -TAz Mixture (51C)>
(Preparation of (HIm) ₃ -TAz)

Heterocycles, 2004, 63, 1897. Was synthesized with reference to FIG. 1.84 g of cyclic chlorolide and 4.08 g of imidazole were added and stirred at 70 ° C. for 2 minutes. The solid was extracted and washed with chloroform and distilled water. The organic layer was dried over sodium sulfate, the solvent was distilled off, and the obtained solid was recrystallized from ethyl acetate to obtain 2.4 g of (HIm) ₃ -TAz.

Molecular formula: C ₁₂ H ₉ N ₉ , molecular weight: 279.26
Elemental analysis (calculated values): C, 51.61, H, 3.25, N, 45.14

(FeAA2, iron (II) chloride tetrahydrate added (HIm) ₃ -TAz mixture preparation)
After adding (HIm) ₃ -TAz 6.30 g, FeAA2 0.403 g, and iron (II) chloride tetrahydrate 6.30 g, mechanically pulverized and mixed to add FeAA2 and iron (II) chloride tetrahydrate. A (HIm) ₃ -TAz mixture (51A) was obtained.

(Infusibilization and carbonization treatment)
FeA2 and iron chloride (II) tetrahydrate added (HIm) ₃ -TAz mixture (51A) 3.1936 g was weighed into a quartz boat and inserted into a tubular furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz It was installed in the center of the tube and nitrogen was circulated at 200 mL / min for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (51B) 0.8524g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (51B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.5107 g of acid-washed carbon material (51C). The obtained acid cleaned carbon material (51C) was used as the nitrogen-containing carbon alloy of Example 51. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 51 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 61)
<FeAA2, iron chloride (II) tetrahydrate added (HIm) ₃ -TAz mixture carbon material refiring and acid treatment (61C)>
(Infusibilization and carbonization treatment, firing method C, vacuum gas displacement rotary furnace)
Weighing 0.3101 g of the acid-cleaned carbon material of Example 51 (51C) into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour, and the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon material (61B) 0.2077g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (61B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and then left overnight to obtain 0.1959 g of an acid cleaned carbon material (61C). The obtained acid cleaned carbon material (61C) was used as the nitrogen-containing carbon alloy of Example 61. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 61 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 52)
<Carbon Material Synthesis of FeAA2, Iron (II) Chloride Tetrahydrate Added 1,2- (4-Py) 2-Ethane Mixture (52C)>

(Preparation of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethane mixture)
1,2- (4-Py) 2-Ethane 6.30 g (manufactured by ALDRICH), FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g were added, and then mechanically pulverized and mixed to obtain FeAA2, chloride. An iron (II) tetrahydrate-added 1,2- (4-Py) 2-Ethane mixture (52A) was obtained.

Molecular formula: C ₁₂ H ₁₀ N ₂ , molecular weight: 182.22
Elemental analysis (calculated values): C, 79.10, H, 5.53, N, 15.37

(Infusibilization and carbonization treatment)
3. 1984 g of FeAA2, iron chloride (II) tetrahydrate added 1,2- (4-Py) 2-Ethane mixture (52A) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter) It was installed at the center of a quartz tube of 3.6 cmφ, and nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (52B) 0.6158g.

(Crushing, water washing treatment, specific surface area measurement)
The carbon material (52B) was pulverized in an agate mortar, washed with water, filtered and air-dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain a non-acid cleaned carbon material (52C). The obtained non-acid cleaned carbon material (52C) was used as the nitrogen-containing carbon alloy of Example 52. The specific surface area was measured by the BET method. The results are shown in the column before acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 52 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 53)
<Carbon Material Synthesis of FeAA2, Iron (II) Chloride Tetrahydrate Added 1,2- (4-Py) 2-Ethane Mixture (53C)>

(Crushing, acid cleaning treatment, specific surface area measurement)
The above-mentioned non-acid-cleaned carbon material (52C) was pulverized in an agate mortar, and concentrated hydrochloric acid cleaning, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.4505 g of acid-cleaned carbon material (53C). The obtained acid cleaned carbon material (53C) was used as the nitrogen-containing carbon alloy of Example 53. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 53 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 62)
<Refiring and acid treatment of carbon material of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethane mixture (62C)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement furnace)
0.1546 g of the acid-cleaned carbon material (53C) of Example 53 was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement rotary furnace. Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (62B) 0.1338g.

(Crushing, water washing treatment, specific surface area measurement)
The carbon material (62B) was pulverized with an agate mortar, washed with water, filtered and air-dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left as it was overnight to obtain a non-acid cleaned carbon material (62C). The obtained non-acid cleaned carbon material (62C) was used as the nitrogen-containing carbon alloy of Example 62. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 62 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 63)
<Refiring and acid treatment (63C) of carbon material of FeAA2, iron (II) chloride tetrahydrate added 1,2- (4-Py) 2-Ethane mixture>

(Crushing, acid cleaning treatment, specific surface area measurement)
The above-mentioned non-acid-cleaned carbon material (62C) was pulverized in an agate mortar, and concentrated hydrochloric acid cleaning, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.1109 g of an acid cleaned carbon material (63C). The obtained acid cleaned carbon material (63C) was used as the nitrogen-containing carbon alloy of Example 63. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 63 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 54)
<Carbon Material Synthesis of Poly (4-VinylPyridine) Mixture with FeAA2, Iron Chloride (II) Tetrahydrate Addition (54C)>

(Preparation of a mixture of FeAA2 and iron (II) chloride tetrahydrate added Poly (4-VinylPyridine))
Poly (4-VinylPyridine) 6.30 g (manufactured by ALDRICH, manufacturer code 523291), FeAA2 0.403 g, iron (II) chloride tetrahydrate 6.30 g were added, then mechanically pulverized and mixed, FeAA2, iron chloride (II) A tetrahydrate-added poly (4-vinylpyridine) mixture (54A) was obtained.

Molecular formula: (C ₇ H ₇ N ₁ ) _n , formula weight: 105.14
Molecular weight: Mw (weight average molecular weight) 5000, Mn (number average molecular weight) 4800, molecular weight distribution (dispersity = weight average molecular weight / number average molecular weight) 1.04.
Elemental analysis (calculated values): C, 79.97, H, 6.71, N, 13.32.

(Infusibilization and carbonization treatment)
Fea2 and iron chloride (II) tetrahydrate added Poly (4-VinylPyridine) mixture (54A) 3.1925 g was measured into a quartz boat and inserted into a tube furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz. It was installed in the center of the tube, and nitrogen was circulated at 200 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (54B) 1.3570g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (54B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.6881 g of acid-washed carbon material (54C). The obtained acid cleaned carbon material (54C) was used as the nitrogen-containing carbon alloy of Example 54. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Example 54 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

(Example 64)
<Refiring and acid treatment (64C) of carbon material of a mixture of FeAA2, iron chloride (II) tetrahydrate added Poly (4-VinylPyridine)>
(Infusibilization and carbonization treatment, firing method B, vacuum gas replacement furnace)
Weighing 0.3244 g of the acid-cleaned carbon material of Example 54 (54C) into a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, Nitrogen was circulated at 200 mL per minute for 1 minute at room temperature. Next, the inside of the tube was evacuated with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (64B) 0.2626g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (64B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.2116 g of acid-cleaned carbon material (64C). The obtained acid cleaned carbon material (64C) was used as the nitrogen-containing carbon alloy of Example 64. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 2 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 16 except that the obtained nitrogen-containing carbon alloy material of Example 64 was used, and the ORR activity value was measured. The results are shown in Table 2 below.

In the case of high molecular weight (Mw 60 × 10 ³ , 160 × 10 ³ ), Poly (4-VinylPyridine) using 2% Divine Benzene or 10% Ethyl Vinyl Benzene as a cross-linking agent (both manufactured by ALDRICH), similarly, by the BET method It was confirmed by ORR measurement using an electrode coated with a specific surface area of 800 m ² / g or more and 0.5 mg / cm ² that the voltage at -1 mA / cm ² was 0.7 V or more.

(Comparative Example 1)
<Synthesis of carbon material of iron chloride (II) tetrahydrate added PhCN mixture (C1C)>
(Preparation of PhCN mixture containing iron (II) chloride tetrahydrate)
6.30 g of PhCN (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.30 g of iron (II) chloride tetrahydrate were mixed and the PhCN mixture added with iron (II) chloride tetrahydrate was calcined, but no carbide was obtained. .

(Comparative Example 2)
<Synthesis of carbon material of iron (II) chloride tetrahydrate added 2-PyCN mixture (C2C)>
(Preparation of 2-PyCN mixture containing iron (II) chloride tetrahydrate)
1.60 g of 2-PyCN (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.60 g of iron (II) chloride tetrahydrate are added and mixed, and then the iron (II) chloride tetrahydrate added 2-PyCN mixture (C2A) is added. Obtained.

Molecular formula: C ₆ H ₄ N ₂ , molecular weight: 104.11.
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Infusibilization and carbonization treatment)
3.0820 g of iron (II) chloride tetrahydrate added 2-PyCN mixture (C2A) was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. Then, nitrogen was circulated at 300 mL / min for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C2B) 0.4897g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (C2B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.0709 g of acid-cleaned carbon material (C2C). The obtained acid cleaned carbon material (C2C) was used as the nitrogen-containing carbon alloy of Comparative Example 2. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Comparative Example 2 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 3)
<Synthesis of carbon material of iron (II) tetrahydrate added 4-PyCN mixture (C3C)>
(Preparation of iron (II) chloride tetrahydrate added 4-PyCN mixture)
4-PyCN 1.60 g (manufactured by Tokyo Chemical Industry Co., Ltd.), iron (II) chloride tetrahydrate 1.60
After adding g, it was mechanically pulverized and mixed to obtain an iron (II) chloride tetrahydrate added 4-PyCN mixture (C3A).

Molecular formula: C ₆ H ₄ N ₂ , molecular weight: 104.11.
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Infusibilization and carbonization treatment)
Weighing 3.0242 g of iron (II) chloride tetrahydrate added 4-PyCN mixture (C3A) in a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. Then, nitrogen was circulated at 300 mL / min for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon material (C3B) 2.9133g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (C3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight as it was to obtain 0.0696 g of acid-cleaned carbon material (C3C). The obtained acid cleaned carbon material (C3C) was used as the nitrogen-containing carbon alloy of Comparative Example 3. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Comparative Example 3 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 4)
<Synthesis of carbon material of FeAA2, iron (II) chloride tetrahydrate added Ph ₃ -TAz mixture (C4C)>
(Preparation of FeAA2, iron (II) chloride tetrahydrate added Ph ₃ -TAz mixture)
Ph ₃ -TAz 6.30 g (manufactured by Sigma-Aldrich), FeAA2 0.403 g,
After adding 6.30 g of iron (II) chloride tetrahydrate, it was mechanically pulverized and mixed to obtain a FeAA2 and iron (II) chloride tetrahydrate added Ph ₃ -TAz mixture (C4A).

Molecular formula: C ₂₁ H ₁₅ N ₃ , molecular weight: 309.36
Elemental analysis (calculated values): C, 81.53, H, 4.89, N, 13.58

(Infusibilization and carbonization treatment)
We measured 3.1811 g of FeAA2, iron chloride (II) tetrahydrate added Ph ₃ -TAz mixture (C4A) in a quartz boat and inserted it into a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was installed in the center and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C4B) 0.2199g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (C4B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.0107 g of acid-washed carbon material (C4C). The obtained acid cleaned carbon material (C4C) was used as the nitrogen-containing carbon alloy of Comparative Example 4. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Comparative Example 4 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 5)
<Carbon Material Synthesis of Iron (II) Chloride Tetrahydrate Addition (4-HN ₂ Ph) ₃ -TAz Mixture (C5C)>
(Preparation of (4-HN ₂ Ph) ₃ -TAz)
(4-HN ₂ Ph) ₃ -TAz was adjusted with reference to International Publication No. 2004 / 106311A2. 31.7 g of trifluoroacetic acid was dissolved in 50 mL of chloroform, added dropwise to 25 g of 4-aminophenylbenzonitrile, and stirred at room temperature for 24 hours. Liquid separation was performed, and the lower layer was added dropwise to ice water. The produced solid was filtered, washed with water and dried to obtain 9.8 g of (4-HN ₂ Ph) ₃ -TAz.
(Addition of iron (II) chloride tetrahydrate (4-HN ₂ Ph) ₃ -TAz mixture) (4-HN ₂
Ph) ₃ -TAz 6.30 g (added iron chloride (II) tetrahydrate 6.30 g, mechanically pulverized and mixed, added iron chloride (II) tetrahydrate (4-HN ₂ Ph) ₃ A TAz mixture (C5A) was obtained.

Molecular formula: C ₂₁ H ₁₈ N ₆ , molecular weight: 354.41
Elemental analysis (calculated values): C, 71.17, H, 5.12, N, 23.71

(Infusibilization and carbonization treatment)
2.5315 g of iron (II) chloride tetrahydrate added (4-HN ₂ Ph) ₃ -TAz mixture (C5A) was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C5B) 0.9188g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (C5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C5C). The obtained acid-washed carbon material (C5C) was used as the nitrogen-containing carbon alloy of Comparative Example 5. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Comparative Example 5 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 6)
<Synthesis of carbon material of FeAA2, iron chloride (II) tetrahydrate added (2-Py) ₃ -TAz mixture (C6C)>

(FeAA2, iron chloride (II) tetrahydrate added (2-Py) ₃ -TAz mixture preparation)
(2-Py) ₃ -TAz 6.30 g (manufactured by SIGMA ALDRICH), FeAA2 0.403 g and iron (II) chloride tetrahydrate 6.30 g were added and then mechanically pulverized and mixed to obtain FeAA2 and iron chloride (II ) Tetrahydrate added (2-Py) ₃ -TAz mixture (C6A) was obtained.

Molecular formula: C ₁₈ H ₁₂ N ₆ , molecular weight: 312.33
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Infusibilization and carbonization treatment)
FeAA2, iron chloride (II) tetrahydrate added (2-Py) ₃ -TAz mixture (C6A) 3.1901 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) In the center of the quartz tube, nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at a rate of 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C6B) 1.6200g.

(Crushing, acid cleaning treatment, specific surface area measurement)
The carbon material (C6B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and allowed to stand overnight to obtain 1.1290 g of acid-washed carbon material (C6C). The obtained acid cleaned carbon material (C6C) was used as the nitrogen-containing carbon alloy of Comparative Example 6. The specific surface area was measured by the BET method. The results are shown in the column after acid cleaning in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the obtained nitrogen-containing carbon alloy material of Comparative Example 6 was used, and the ORR activity value was measured. The results are shown in Table 1 below.

From Table 1 above, the nitrogen-containing carbon alloys of Examples 1-28, Examples 30-36, Examples 40-46, Examples 50-54 and Examples 60-64 have a sufficiently large specific surface area and show catalyst performance. It was found that the ORR voltage shown was sufficiently high. Furthermore, it was found that the yield of nitrogen-containing carbon alloy was also good. Further, it was found that a higher ORR voltage was obtained in the nitrogen-containing carbon alloy to which the organometallic complex was added during the production.
It can also be seen that a higher ORR voltage is obtained by providing a re-baking step. Furthermore, the yield is improved by providing a re-baking step.
On the other hand, it was found that the comparative example had an insufficient increase in specific surface area and had a low voltage indicating catalyst performance, which was insufficient.

(Fuel cell power generation performance evaluation)
(1) Preparation of catalyst ink (1) -1 Preparation of cathode catalyst ink (28E) 0.1 g of nitrogen-containing carbon alloy material (28C) of Example 28, 1.0 g of 5% by mass Nafion (registered trademark) Disperse the solution (solvent: mixture of water and lower alcohol, WAKO number 321-86703), 0.25 mL of water (ion-exchanged water), and 0.5 mL of 1-propanol for 2.5 hours with an ultrasonic disperser. A non-platinum catalyst ink for cathode (28E) was obtained.

(1) -2 Preparation of anode catalyst ink 0.5 g of platinum-supported carbon (TEC10V50E, manufactured by Tanaka Kikinzoku Co., Ltd.) carrying 50% by mass of platinum was weighed in a glass container, and 0.8 mL of water was added. After the addition, the glass container was sealed with a septum seal, and the inside of the container was purged with nitrogen. The catalyst ink for anode was obtained by inject | pouring 4.3 mL of 5 mass% Nafion mentioned above and 1 mL of 1-propanol in a glass container, and irradiating an ultrasonic wave for 2.5 hours.

(2) Preparation of transfer catalyst coating film (2) -1 Preparation of cathode catalyst film (1) Cathode catalyst ink prepared in (1) -1 was applied on a Teflon (registered trademark) sheet base with a 200 μm clearance applicator. It was applied and slowly dried over 24 hours. After drying, it was cut into a 5 cm × 5 cm size square. The coating weight obtained by subtracting the base weight from the weight of the coating film was 47.6 mg (1.9 mg / cm ² ).

(2) -2 Preparation of anode catalyst membrane The anode catalyst ink prepared in (1) -2 was applied on a Teflon (registered trademark) sheet base with a 300 μm clearance applicator and slowly dried over 24 hours. It was. After drying, it was cut into a 5 cm × 5 cm size square. The weight of the coated product obtained by subtracting the base weight from the weight of the coated film was 21.5 mg (0.86 mg / cm ² ).

(3) Preparation of transfer proton conducting membrane A Nafion membrane (NR211, manufactured by DuPont) cut into a square of 8 cm x 8 cm size was immersed in a 1 mol / L CsCl aqueous solution for 10 hours and washed with ion-exchanged water. Thereafter, it was dried to obtain a proton conductive membrane for transfer.

(4) Preparation of electrode composite membrane Between two polyimide membranes (UPILEX 75: manufactured by Ube Industries Co., Ltd.) cut into 10 cm x 10 cm squares, the catalyst membrane prepared in (2) -1; (3) The prepared proton conducting membrane and the catalyst membrane prepared in (2) -2 were superposed in this order. At this time, the catalyst membrane was at the center of the proton conducting membrane, and the coating surface was in contact with the ptrone conducting membrane. The laminated sheet was pressed at 210 ° C. and 15 MPa for 10 minutes. The thermocompression-bonded film was taken out from the two polyimide films, and the catalyst layer was transferred to both sides of the proton conducting film by peeling off the Teflon (registered trademark) sheet which is the base of the cathode coating film and the anode coating film. An electrode composite membrane was obtained. This electrode composite membrane was immersed in a 0.5 mol / L sulfuric acid aqueous solution for 10 hours, washed with ion-exchanged water, and dried to obtain the desired electrode composite membrane.

(5) Assembly of fuel cell for evaluation The electrode composite membrane obtained in (4) is sandwiched between two carbon cloths (made by gas diffusion layer ELAT BASF) cut into a square of 5 cm × 5 cm size, and a gasket having a thickness of 200 μm (Made by Tepron) was incorporated into a JARI standard cell (manufactured by FC Development Co., Ltd.) to obtain a fuel cell (Cell-1) having a catalyst effective area of 25 cm ² .

(6) Power generation performance evaluation While keeping the fuel cell at 80 ° C., humidified hydrogen was supplied to the anode and humidified air was supplied to the cathode. Hydrogen and air were humidified by passing each gas through a bubbler containing water. The water temperature of the hydrogen bubbler was 80 ° C, and the water temperature of the air bubbler was 80 ° C. Here, the hydrogen gas flow rate was 1000 ml / min, the air gas flow rate was 2500 ml / min, and measurement was performed under normal pressure.
A current-voltage curve was obtained by changing the current value of the fuel cell from 0 A to 7.5 A every 30 seconds and measuring a stable voltage at each current.

  Non-platinum catalyst ink for cathode (21E) prepared from the nitrogen-containing carbon alloy material of the present invention in place of the modified product (28E) used in (1) -1 in the same procedure as (1) to (5) above. ), (24E), (27E), and comparative carbon material inks for cathodes (C3E) and (C5E), and assembling evaluation batteries (Cell-2) to (Cell-6), and (6) Similarly, current-voltage measurement was performed. The voltage at a current value of 2A is shown in Table 2.

  According to the present invention, a nitrogen-containing carbon alloy having a sufficiently high oxygen reduction activity can be obtained. For this reason, the nitrogen-containing carbon alloy obtained by the production method of the present invention can be used as a carbon catalyst. Moreover, according to the manufacturing method of this invention, the yield of a nitrogen-containing carbon alloy can be raised and productivity can be improved. Such a carbon catalyst is preferably used for a fuel cell or an environmental catalyst and has high industrial applicability.

10 Fuel cell,
12 separator,
13 Anode electrocatalyst,
14 solid polymer electrolyte,
15 cathode catalyst,
16 separator,
20 electric double layer capacitor,
21 first electrode;
22 second electrode,
23 separator,
24a exterior lid,
24b exterior case,
25 Current collector,
26 Gasket

Claims (25)

Including a step of firing a precursor containing an inorganic metal salt and at least one selected from a heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the following general formula (1), a salt thereof and a hydrate thereof A method for producing a nitrogen-containing carbon alloy;

In general formula (1), A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring, L represents a single bond or a (x + 1) -valent linking group, and B represents a hydrogen atom, a substituted or Represents an unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups , Any one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X and y each independently represents an integer of 1 or more.   In the said General formula (1), x represents the integer of 1-3, y represents the integer of 1-5, The manufacturing method of the nitrogen-containing carbon alloy of Claim 1. The method for producing a nitrogen-containing carbon alloy according to claim 1 or 2, wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is represented by the following general formula (2);

In General Formula (2), Q ^{1 to} Q ³ each independently represents a hetero atom or a carbon atom, at least one of Q ^{1 to} Q ³ is a nitrogen atom, b1 to b3 are each independently a hydrogen atom, Represents a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of b1 to b3 is a substituted or unsubstituted nitrogen-containing aromatic group, and a nitrogen-containing aromatic group In at least one of the groups, one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the binding site are nitrogen atoms. Q Number heteroatoms in non-fused heteroaromatic ring containing ¹ to Q ³ is or greater identical to the number of heteroatoms in the nitrogen-containing aromatic group per one of b1 to b3. In the general formula (2), Q ¹ ~Q ³ the method of manufacturing the nitrogen-containing carbon alloy of claim 3 is a nitrogen atom.   In the said General formula (2), b1-b3 is a 6-membered substituted or unsubstituted nitrogen-containing aromatic group, The manufacturing method of the nitrogen-containing carbon alloy of Claim 3 or 4.   In the said General formula (2), b1-b3 is a pyridyl group or a pyrimidyl group, The manufacturing method of the nitrogen-containing carbon alloy of any one of Claims 3-5. The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 6, wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group is a compound represented by the following formula (3) or (4). .

The method for producing a nitrogen-containing carbon alloy according to claim 1 or 2, wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) is represented by the following general formula (5);

In general formula (5), A represents an atomic group composed of a 5- to 11-membered non-condensed heteroaromatic ring, L represents a single bond or a (x + 1) -valent linking group, B represents a hydrogen atom, substituted Or an unsubstituted aromatic group or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups In the above, any one or both of the ring skeleton constituting atoms at the 3rd and 4th positions relative to the bonding site with L are nitrogen atoms. The number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B. X represents an integer of 1 or more.   In the said General formula (5), x represents the integer of 1-5, The manufacturing method of the nitrogen-containing carbon alloy of Claim 8. The method for producing a nitrogen-containing carbon alloy according to claim 1 or 2, wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group is a compound selected from the following compound group.

  The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 10, wherein the inorganic metal salt is an inorganic metal chloride.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 11, wherein the metal species of the inorganic metal salt is Fe or Co.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 12, wherein the inorganic metal salt is a hydrate salt.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 13, further comprising an organometallic complex.   The method for producing a nitrogen-containing carbon alloy according to claim 14, wherein the organometallic complex is a metal acetate complex or a β-diketone metal complex.   The method for producing a nitrogen-containing carbon alloy according to claim 14 or 15, wherein the organometallic complex is an acetylacetone iron (II) complex.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 16, wherein the firing step is a step of firing the precursor at 400 ° C or higher.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 17, wherein the firing step is a step of firing the precursor at 700 to 1000 ° C.   The manufacturing method of the nitrogen-containing carbon alloy of any one of Claims 1-18 which further includes the process of grind | pulverizing the said precursor before the said baking process.   The manufacturing method of the nitrogen-containing carbon alloy of any one of Claims 1-19 including the acid washing | cleaning process of wash | cleaning the baked nitrogen-containing carbon alloy with an acid after the said baking process.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 20, further comprising a step of pulverizing the baked nitrogen-containing carbon alloy and a step of re-baking after the calcination step.   The method for producing a nitrogen-containing carbon alloy according to claim 21, wherein the re-baking step is a step of baking at 1000 to 1500 ° C.   The method for producing a nitrogen-containing carbon alloy according to claim 21 or 22, further comprising a step of deaeration and nitrogen substitution before the re-firing step.   The nitrogen-containing carbon alloy manufactured by the method of any one of Claims 1-23.   A fuel cell catalyst using the nitrogen-containing carbon alloy according to claim 24.

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